Pesticidally active heterocyclic derivatives with sulphur containing substituents

ABSTRACT

Compounds of formula (I), wherein the substituents are as defined in claim  1 , and the agrochemically acceptable salts salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, can be used as insecticides and can be prepared in a manner known per se.

The present invention relates to insecticidally active heterocyclicderivatives containing sulphur substituents, to processes for theirpreparation, to compositions comprising those compounds, and to theiruse for controlling animal pests (including arthropods and in particularinsects or representatives of the order Acarina).

Heterocyclic compounds with pesticidal action are known and described,for example, in WO 2010/125985 and WO 2013/018928.

There have now been found novel pesticidally active heterocyclictriazole derivatives with sulphur containing phenyl- and pyridylsubstituents.

The present invention accordingly relates to compounds of formula I,

wherein

G₁ is nitrogen or CR₂;

G₂ is nitrogen or CR₃;

G₃ is nitrogen or CR₄;

G₄ is nitrogen or CR₅;

G₅ is nitrogen or CR₆, with the proviso that not more than 2 nitrogensas G may follow consecutively;

R₂, R₃, R₄, R₅ or R₆ are, independently from each other, hydrogen,halogen, C₁-C₄haloalkyl, C₁-C₄haloalkyl substituted by one or twohydroxy, C₁-C₄haloalkyl substituted by one or two methoxy,C₁-C₄haloalkyl substituted by one or two cyano; or

R₂, R₃, R₄, R₅ or R₆ are, independently from each other,C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅,phenylcarbonylthio, cyano, mercapto, C₁-C₄alkoxycarbonyl, or—C(O)C₁-C₄haloalkyl; or

two adjacent R_(i), wherein R_(i) is selected from R₂, R₃, R₄, R₅ andR₆, taken together may form a fragment —OCH₂O— or —OCF₂O—;

Q is a radical selected from the group consisting of formula Q₁ to Q₂

wherein the arrow denotes the point of attachment to the triazole ring;

and wherein X is S, SO or SO₂;

each R is, independently from each other, hydrogen, halogen,C₁-C₄haloalkoxy or C₁-C₄haloalkyl;

each R₁ is, independently from each other, C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and

each R₇ is, independently from each other, hydrogen or halogen; and

R₈ is hydrogen, C₁-C₄alkyl or C₁-C₄haloalkyl; and agrochemicallyacceptable salts, stereoisomers, enantiomers, tautomers and N-oxides ofthose compounds; with the exception of2-[5-(2,4-dichlorophenyl)-4-methyl-1,2,4-triazol-3-yl]-3-methylsulfanyl-pyridine;2-[5-(2,4-dichlorophenyl)-4-methyl-1,2,4-triazol-3-yl]-3-ethylsulfanyl-pyridine;and2-[5-(4-n-pentylphenyl)-4-methyl-1,2,4-triazol-3-yl]-3-methylsufonyl-pyridine.

Compounds of formula I which have at least one basic centre can form,for example, acid addition salts, for example with strong inorganicacids such as mineral acids, for example perchloric acid, sulfuric acid,nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, withstrong organic carboxylic acids, such as C₁-C₄alkanecarboxylic acidswhich are unsubstituted or substituted, for example by halogen, forexample acetic acid, such as saturated or unsaturated dicarboxylicacids, for example oxalic acid, malonic acid, succinic acid, maleicacid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids,for example ascorbic acid, lactic acid, malic acid, tartaric acid orcitric acid, or such as benzoic acid, or with organic sulfonic acids,such as C₁-C₄alkane- or arylsulfonic acids which are unsubstituted orsubstituted, for example by halogen, for example methane- orp-toluenesulfonic acid. Compounds of formula I which have at least oneacidic group can form, for example, salts with bases, for examplemineral salts such as alkali metal or alkaline earth metal salts, forexample sodium, potassium or magnesium salts, or salts with ammonia oran organic amine, such as morpholine, piperidine, pyrrolidine, a mono-,di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- ordimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, forexample mono-, di- or triethanolamine.

The alkyl groups occurring in the definitions of the substituents can bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl,hexyl, nonyl, decyl and their branched isomers. Alkoxy, alkenyl andalkynyl radicals are derived from the alkyl radicals mentioned. Thealkenyl and alkynyl groups can be mono- or polyunsaturated.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy groups preferably have a preferred chain length of from 1 to 6carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy,i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also theisomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.

Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbonatoms.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl orisopropoxyethyl.

The cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, forexample cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

According to the present invention, O(C₁-C₄haloalkyl) is equivalent toC₁-C₄haloalkoxy. Haloalkoxy groups preferably have a chain length offrom 1 to 4 carbon atoms. Haloalkoxy is, for example, difluoromethoxy,trifluoromethoxy or 2,2,2-trifluoroethoxy.

According to the present invention, when two adjacent R_(i), whereinR_(i) is selected from R₂, R₃, R₄, R₅ and R₆, taken together form afragment —OCH₂O— or —OCF₂O— then an additional five-membered dioxolaneor difluoro-dioxolane ring is formed. For example, a compound of formulaI, wherein G₂ is CR₃, G₃ is CR₄ and in which R₃ and R₄ taken togetherform the fragment —OCF₂O—, has the following structure:

According to the present invention, when two groups G are nitrogen thenthe radical consisting of G₁ to G₅ together with the carbon atom towhich G₁ and G₅ are attached form a diazine ring. The diazine ring maybe selected from the group consisting of pyrimidinyl, pyrazinyl andpyridazinyl.

In a preferred group of compounds of formula I,

R₂, R₃, R₄, R₅ or R₆ are, independently from each other, hydrogen,halogen, C₁-C₄haloalkyl, C₁-C₄haloalkyl substituted by one or twohydroxy, C₁-C₄haloalkyl substituted by one or two methoxy; or

R₂, R₃, R₄, R₅ or R₆ are, independently from each other,C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfonyl, O(C₁-C₄haloalkyl), SF₅,phenylcarbonylthio, cyano, mercapto or C₁-C₄alkoxycarbonyl and each Ris, independently from each other, hydrogen, halogen or C₁-C₄haloalkyl.

A preferred group of compounds of formula I is represented by thecompounds of formula I-1

wherein G₁, G₂, G₃, G₄, and G₅ are as defined under formula I above; andwherein X₁ is S, SO or SO₂;

Ra₁ is hydrogen, halogen or C₁-C₄haloalkyl; and R₁₁ is methyl, ethyl,n-propyl, i-propyl or cyclopropylmethyl; R₈ is as defined above underformula I, preferably methyl, and agrochemically acceptable salts,stereoisomers, enantiomers, tautomers and N-oxides of those compounds.

In a preferred embodiment of the invention, the compound of formula I isrepresented by the compounds of formula I-1 wherein G₁ is N, G₂ is CH,G₃ is CH, G₄ is C(CF₃) and G₅ is CH or G₁ is CH, G₂ is N, G₃ is CH, G₄is C(CF₃) and G₅ is CH.

Preferred compounds of formula I-1 have G₁, G₂, G₄ and G₅ defined as CH,and G₃ defined as C(CF₃). Other preferred compounds of formula I-1 haveG₁, G₃, G₄ and G₅ defined as CH, and G₂ defined as C(CF₃).

Also preferred are compounds of formula I-1 with G₁ defined as N, G₂defined as C(CF₃), and G₃, G₄ and G₅ defined as CH.

Yet other preferred compounds of formula I-1 have G₁ defined as N, G₃defined as C(CF₃), and G₂, G₄ and G₅ defined as CH.

Further preferred compounds of formula I-1 have G₁ defined as N, G₄defined as C(CF₃), and G₂, G₃ and G₅ defined as CH.

Other preferred compounds of formula I-1 have G₁, G₄ and G₅ defined asCH, G₂ defined as N and G₃ defined as C(CF₃).

Also preferred are compounds of formula I-1 with G₁, G₃ and G₅ definedas CH, G₂ defined as N and G₄ defined as C(CF₃).

Yet other preferred compounds of formula I-1 have G₁, G₄ and G₅ definedas CH, G₃ defined as N and G₂ defined as C(CF₃).

Another group of preferred compounds of formula I-1 have G₁ and G₃defined as N, G₄ and G₅ defined as CH, and G₂ defined as C(CF₃).

Other preferred compounds of formula I-1 have G₁ and G₄ defined as N, G₂and G₅ defined as CH, and G₃ defined as C(CF₃).

Also preferred are compounds of formula I-1 with G₁ and G₄ defined as N,G₃ and G₅ defined as CH, and G₂ defined as C(CF₃).

Yet other preferred compounds of formula I-1 have G₁ and G₅ defined asN, G₂ and G₄ defined as CH, and G₃ defined as C(CF₃).

Further preferred compounds of formula I-1 have G₁ and G₅ defined as N,G₃ and G₄ defined as CH, and G₂ defined as C(CF₃).

Other preferred compounds of formula I-1 have G₂ and G₄ defined as N, G₁and G₅ defined as CH, and G₃ defined as C(CF₃).

Also preferred are compounds of formula I-1 with G₁ and G₂ defined as N,G₄ and G₅ defined as CH, and G₃ defined as C(CF₃).

Yet other preferred compounds of formula I-1 have G₁ and G₂ defined asN, G₃ and G₅ defined as CH, and G₄ defined as C(CF₃).

In further preferred compounds of formula I-1, G₁ and G₃ are N, G₂ andG₅ are CH, and G₄ is C(CF₃).

In an especially preferred group of compounds of formula I-1, G₁ is N,G₂ is CH or C(halogen), G₃ is CH, G₄ is C(CF₃) and G₅ is CH.

In an especially preferred group of compounds of formula I-1, G₁ is CH,G₂ is N, G₃ is CH, G₄ is C(CF₃) or C(CN) and G₅ is CH.

In an especially preferred group of compounds of formula I-1, G₁ is CH,G₂ is N, G₃ is C(CF₃), C(CN) or C(halogen), G₄ is CH and G₅ is CH.

In an especially preferred group of compounds of formula I-1, G₁ is CH,G₂ is CH, G₃ is N, G₄ is C(CF₃) or C(halogen) and G₅ is CH.

In an especially preferred group of compounds of formula I-1, G₁ is N,G₂ is CH, G₃ is C(CF₃), G₄ is CH and G₅ is CH.

In an especially preferred group of compounds of formula I-1, G₁ is N,G₂ is C(CF₃) or C(CN), G₃ is CH, G₄ is CH and G₅ is CH.

In an especially preferred group of compounds of formula I-1, G₁ is CH,G₂ is CH, G₃ is C(CF₃), C(OCF₃), C(CN) or C(halogen), G₄ is CH and G₅ isCH.

In an especially preferred group of compounds of formula I-1, G₁ is CH,G₂ is C(CF₃), C(OCF₃), C(CN) or C(halogen), G₃ is CH, G₄ is CH and G₅ isCH. In said especially preferred group of compounds of formula I-1, R₈is preferably methyl.

Another preferred group of compounds of formula I is represented by thecompounds of formula I-2

wherein G₁, G₂, G₃, G₄, and G₅ are as defined under formula I above; andwherein X₂ is S, SO or SO₂;

Ra₂ is hydrogen, halogen or C₁-C₄haloalkyl; and R₁₂ is methyl, ethyl,n-propyl,

i-propyl or cyclopropylmethyl; R₈ is as defined above under formula I,preferably methyl, and agrochemically acceptable salts, stereoisomers,enantiomers, tautomers and N-oxides of those compounds.

Preferred compounds of formula I-2 have G₁, G₂, G₄ and G₅ defined as CH,and G₃ defined as C(CF₃).

Other preferred compounds of formula I-2 have G₁, G₃, G₄ and G₅ definedas CH, and G₂ defined as C(CF₃).

Also preferred are compounds of formula I-2 with G₁ defined as N, G₂defined as C(CF₃), and G₃, G₄ and G₅ defined as CH.

Yet other preferred compounds of formula I-2 have G₁ defined as N, G₃defined as C(CF₃), and G₂, G₄ and G₅ defined as CH.

Further preferred compounds of formula I-2 have G₁ defined as N, G₄defined as C(CF₃), and G₂, G₃ and G₅ defined as CH.

Other preferred compounds of formula I-2 have G₁, G₄ and G₅ defined asCH, G₂ defined as N and G₃ defined as C(CF₃).

Also preferred are compounds of formula I-2 with G₁, G₃ and G₅ definedas CH, G₂ defined as N and G₄ defined as C(CF₃).

Yet other preferred compounds of formula I-2 have G₁, G₄ and G₅ definedas CH, G₃ defined as N and G₂ defined as C(CF₃).

Another group of preferred compounds of formula I-2 have G₁ and G₃defined as N, G₄ and G₅ defined as CH, and G₂ defined as C(CF₃).

Other preferred compounds of formula I-2 have G₁ and G₄ defined as N, G₂and G₅ defined as CH, and G₃ defined as C(CF₃).

Also preferred are compounds of formula I-2 with G₁ and G₄ defined as N,G₃ and G₅ defined as CH, and G₂ defined as C(CF₃).

Yet other preferred compounds of formula I-2 have G₁ and G₅ defined asN, G₂ and G₄ defined as CH, and G₃ defined as C(CF₃).

Further preferred compounds of formula I-2 have G₁ and G₅ defined as N,G₃ and G₄ defined as CH, and G₂ defined as C(CF₃).

Other preferred compounds of formula I-2 have G₂ and G₄ defined as N, G₁and G₅ defined as CH, and G₃ defined as C(CF₃).

Also preferred are compounds of formula I-2 with G₁ and G₂ defined as N,G₄ and G₅ defined as CH, and G₃ defined as C(CF₃).

Yet other preferred compounds of formula I-2 have G₁ and G₂ defined asN, G₃ and G₅ defined as CH, and G₄ defined as C(CF₃).

In further preferred compounds of formula I-2, G₁ and G₃ are N, G₂ andG₅ are CH, and G₄ is C(CF₃).

In an especially preferred group of compounds of formula I-2, G₁ is N,G₂ is CH or C(halogen), G₃ is CH, G₄ is C(CF₃) and G₅ is CH.

In an especially preferred group of compounds of formula I-2, G₁ is CH,G₂ is N, G₃ is CH, G₄ is C(CF₃) or C(CN) and G₅ is CH.

In an especially preferred group of compounds of formula I-2, G₁ is CH,G₂ is N, G₃ is C(CF₃), C(CN) or C(halogen), G₄ is CH and G₅ is CH.

In an especially preferred group of compounds of formula I-2, G₁ is CH,G₂ is CH, G₃ is N, G₄ is C(CF₃) or C(halogen) and G₅ is CH.

In an especially preferred group of compounds of formula I-2, G₁ is N,G₂ is CH, G₃ is C(CF₃), G₄ is CH and G₅ is CH.

In an especially preferred group of compounds of formula I-2, G₁ is N,G₂ is C(CF₃) or C(CN), G₃ is CH, G₄ is CH and G₅ is CH.

In an especially preferred group of compounds of formula I-2, G₁ is CH,G₂ is CH, G₃ is C(CF₃), C(OCF₃), C(CN) or C(halogen), G₄ is CH and G₅ isCH.

In an especially preferred group of compounds of formula I-2, G₁ is CH,G₂ is C(CF₃), C(OCF₃), C(CN) or C(halogen), G₃ is CH, G₄ is CH and G₅ isCH. In said especially preferred group of compounds of formula I-2, R₈is preferably methyl.

A further preferred embodiment of the invention comprises compounds offormula I represented by the compounds of formula I-3

wherein

A is N or CH;

R₁₀ is phenyl mono- or polysubstituted by substituents independentlyselected from the group consisting of halogen, cyano, C₁-C₄haloalkoxy,C₁-C₄alkoxycarbonyl or C₁-C₄haloalkyl; or

R₁₀ is phenyl substituted by a fragment OCF₂O on two adjacent positions;or

R₁₀ is pyridyl mono- or polysubstituted by substituents independentlyselected from the group consisting of halogen, cyano, C₁-C₄haloalkoxy orC₁-C₄haloalkyl; or

R₁₀ is pyridyl substituted by a fragment OCF₂O on two adjacentpositions;

X₃ is S, SO or SO₂, in particular S or SO₂;

Ra₃ is hydrogen, C₁-C₄haloalkoxy or C₁-C₄haloalkyl;

R₁₃ is C₁-C₄alkyl or C₃-C₆cycloalkyl-C₁-C₄alkyl, in particular methyl,ethyl or cyclopropylmethyl;

R₈ is hydrogen or C₁-C₄alkyl, in particular methyl or ethyl;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-3.

In said preferred embodiment comprising compounds of formula I-3, R₁₀ ispreferably phenyl or pyridyl monosubstituted by substituentsindependently selected from the group consisting of halogen, cyano,C₁-C₄haloalkoxy or C₁-C₄haloalkyl. Especially preferred is a substituentselected from fluorine, chlorine, cyano, difluoromethoxy,trifluoromethoxy, trifluoromethyl or pentafluoroethyl.

A further preferred embodiment of the invention comprises compounds offormula I represented by the compounds of formula I-4

wherein

A is N or CH;

R₁₀′ is a diazine radical selected from the group consisting of formulaDA1 to DA5,

wherein the arrow denotes the point of attachment to the triazole ring,and said group R₁₀′ may be mono- or polysubstituted by substituentsindependently selected from the group consisting of halogen, cyano,C₁-C₄haloalkoxy or C₁-C₄haloalkyl;

X₄ is S, SO or SO₂, in particular S or SO₂;

Ra₄ is hydrogen, C₁-C₄haloalkoxy or C₁-C₄haloalkyl;

R₁₄ is C₁-C₄alkyl or C₃-C₆cycloalkyl-C₁-C₄alkyl, in particular methyl,ethyl or cyclopropylmethyl;

R₈ is hydrogen or C₁-C₄alkyl, in particular methyl or ethyl;

and agrochemically acceptable salts, stereoisomers, enantiomers,tautomers and N-oxides of the compounds of formula I-4.

In said preferred embodiment comprising compounds of formula I-4, R₁₀′is preferably a diazine radical selected from the group consisting offormula DA1 to DA5 monosubstituted by substituents independentlyselected from the group consisting of halogen, cyano, C₁-C₄haloalkoxy orC₁-C₄haloalkyl. Especially preferred for R₁₀′ is a substituent selectedfrom fluorine, chlorine, cyano, difluoromethoxy, trifluoromethoxy,trifluoromethyl or pentafluoroethyl. Yet further preferred compounds offormula I-4 have R₁₀′ defined as DA5, wherein R₁₀, is monosubstituted bysubstituents independently selected from the group consisting ofhalogen, cyano, C₁-C₄haloalkoxy or C₁-C₄haloalkyl, in particular byfluorine, chlorine, cyano, difluoromethoxy, trifluoromethoxy,trifluoromethyl or pentafluoroethyl.

The process according to the invention for preparing compounds offormula I is carried out in principle by methods known to those skilledin the art. More specifically, the subgroup of compounds of formula I,wherein X is SO (sulfoxide) and/or SO₂ (sulfone), may be obtained bymeans of an oxidation reaction of the corresponding sulfide compounds offormula I, wherein X is S, involving reagents such as, for example,m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide, oxone, sodiumperiodate, sodium hypochlorite or tert-butyl hypochlorite amongst otheroxidants. The oxidation reaction is generally conducted in the presenceof a solvent. Examples of the solvent to be used in the reaction includealiphatic halogenated hydrocarbons such as dichloromethane andchloroform; alcohols such as methanol and ethanol; acetic acid; water;and mixtures thereof. The amount of the oxidant to be used in thereaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, relativeto 1 mole of the sulfide compounds I to produce the sulfoxide compoundsI, and preferably 2 to 2.2 moles of oxidant, relative to 1 mole of thesulfide compounds I to produce the sulfone compounds I. Such oxidationreactions are disclosed, for example, in WO 2013/018928.

The subgroup of compounds of formula I, wherein X is S (sulfide) andwherein Q, R₈, G₁, G₂, G₃, G₄, and G₅ are as defined above,

may be prepared by reacting an amidine compound of formula II, or a saltthereof (such as a hydrohalide salt, preferably a hydrochloride or ahydrobromide salt, or any other equivalent salt), wherein R₈, G₁, G₂,G₃, G₄, and G₅ are as defined above, with a hydrazide compound offormula III, or a salt thereof, wherein Q is as defined above andwherein X is S (sulfide), optionally in presence of a base such asalkali metal carbonates, for example sodium carbonate or potassiumcarbonate, in a solvent such as methanol, ethanol, isopropanol,acetonitrile, N,N-dimethylformamide or N,N-dimethyl-acetamide, attemperatures between 0 and 200° C., preferably between 50 and 150° C.,optionally under microwave irradiation. Such a process may be carriedout in analogy to, for example, G. Bonanomi et al., Chem Med Chem 2010,5, 705-715. The compounds of formula II may be reacted with anyconfiguration (E or Z, or any mixture thereof) on the carbon-nitrogendouble bond.

Compounds of formula II, or a salt thereof (such as a hydrohalide salt,preferably a hydrochloride or a hydrobromide salt, or any otherequivalent salt), wherein R₈, G₁, G₂, G₃, G₄, and G₅ are as definedabove,

may be prepared by reacting a nitrile compound of formula IV, whereinG₁, G₂, G₃, G₄, and G₅ are as defined above,

sequentially with

i) a catalytic amount, preferably 0.01 to 0.5 equivalent, of analkoxide, preferably sodium methoxide NaOMe or sodium ethoxide NaOEt, inan alcoholic solvent, such as methanol or ethanol, at temperaturesbetween 0 and 100° C., to generate an imidate intermediate of theformula INT₁ (or a salt and/or a tautomer thereof); followed by

ii) treatment with an amine reagent of formula V

R₈—NH₂  (V),

or a salt thereof (such as a hydrohalide salt, preferably ahydrochloride or a hydrobromide salt, or any other equivalent salt),wherein R₈ is as defined above, optionally in the presence of an acid(such as a hydrohalide acid, preferably hydrochloric acid or hydrobromicacid, or any other equivalent acid), at temperatures between 0-180° C.,to generate an amidine intermediate of the formula INT₁ (or a saltand/or a tautomer thereof); followed by

iii) treatment with an excess of the amine reagent of formula V, or asalt thereof (such as a hydrohalide salt, preferably a hydrochloride ora hydrobromide salt, or any other equivalent salt), wherein R₈ is asdefined above, preferably in the presence of an acid (such as ahydrohalide acid, preferably hydrochloric acid or hydrobromic acid, orany other equivalent acid), at temperatures between 0-180° C., to formthe compound of the formula II, or a salt and/or a tautomer thereof. Thecompounds of formula II may be isolated with any configuration (E or Z,or any mixture thereof) on the carbon-nitrogen double bond. Steps ii)and iii) may be combined, for example to allow a direct formation of acompound of formula II from a compound of formula INT₁. Steps ii) and/oriii) may also be performed under microwave irradiation, each optionallyalso in a pressurized vessel. Compounds of the formula INT₁ mayalternatively be prepared under conditions and variants of the Pinnerreaction known to a person skilled in the art, typically by treating acompound of the formula IV with a hydrohalide acid, preferablyhydrochloric acid, in presence of alcoholic reagents such as methanol orethanol, preferably in an inert solvent such as diethyl ether,tetrahydrofuran or dioxane, at temperatures between −40 and 50° C.,preferably between −20 and 20° C. The described process to preparecompounds of the formula II from compounds of the formula IV may includeisolation and purification of the intermediates INT₁ and/or INT₂ (whichmay be isolated as free bases or as salts (e.g. a hydrohalide salt, morespecifically a hydrochloride or hydrobromide salt, or any otherequivalent salt)), however this process is advantageously conducted as aone-pot preparation. In the particular situation where R₈ is methyl orethyl, the amine reagent of formula V may be engaged in the abovereaction as a gas, as a salt (such as a hydrohalide salt, preferably ahydrochloride or a hydrobromide salt, or any other equivalent salt), oras a solution in solvents such as methanol, ethanol, tetrahydrofuran orwater.

Compounds of formula IV, wherein G₁, G₂, G₃, G₄, and G₅ are as definedabove, are known compounds or can be prepared by known methods,described in the literature.

Compounds of the formula III, or a salt thereof, wherein Q is as definedabove,

may be prepared by

i) activation of compound of formula VI, wherein Q is as defined above,by methods known to those skilled in the art and described in, forexample, Tetrahedron, 2005, 61 (46), 10827-10852, to form an activatedspecies VIa, wherein Q is as defined above and wherein X₀₀ is halogen,preferably chlorine. For example, compounds VIa where X₀₀ is halogen,preferably chlorine, are formed by treatment of VI with, for example,oxallyl chloride (COCl)₂ or thionyl chloride SOCl₂ in the presence ofcatalytic quantities of N,N-dimethylformamide DMF in inert solvents suchas methylene chloride CH₂Cl₂ or tetrahydrofuran THF at temperaturesbetween 20 to 100° C., preferably 25° C. Alternatively, treatment ofcompounds of formula VI with, for example,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC will generate an activated species VIa, wherein X₀₀ isX₀₁ or X₀₂ respectively, in an inert solvent, such as pyridine ortetrahydrofuran THF, optionally in the presence of a base, such astriethylamine, at temperatures between 50-180° C.; followed by

ii) Treatment of the activated species VIa with hydrazine NH₂NH₂ (or asalt thereof), possibly in form of a hydrate, preferably hydrazinemonohydrate, optionally in the presence of a base, such as triethylamineor pyridine, in an inert solvents such as dichloromethane,tetrahydrofuran, dioxane or toluene, at temperatures between 0 and 50°C., to form the compounds of formula III.

Alternatively, compounds of the formula III, or a salt thereof, whereinQ is as defined above, may be prepared by the direct action of hydrazine(or a salt thereof), possibly in form of a hydrate, preferably hydrazinemonohydrate, on an ester derivative VIb

of the compound of formula VI, wherein Q is as defined above and whereinR₀₀ is C₁-C₄alkyl, preferably methyl or ethyl, at temperatures between20 and 150° C. Such a process description may be found, for example, inM. H. Klingele et al, Eur. J. Org. Chem. 2004, 3422-3434.

Compounds of formula VI and VIb, wherein Q is as defined above, areknown compounds or can be prepared by known methods, described in theliterature.

Compounds of formula I, wherein Q, R₈, G₁, G₂, G₃, G₄, and G₅ are asdefined in formula I and wherein X is S (sulfide),

can also be prepared by reacting a compound of formula VII, wherein R₈,G₁, G₂, G₃, G₄, and G₅ are as described in formula I and wherein Q_(a)is a radical selected from the group consisting of formula Q_(1a) toQ_(2a):

wherein R and R₇ are as defined in formula I, and wherein X₁₀ is ahalogen,

with a compound of formula VIII

R₁—SH  (VIII),

or a salt thereof, wherein R₁ is as defined in formula I, optionally inthe presence of a suitable base, such as alkali metal carbonates, forexample sodium carbonate and potassium carbonate, or alkali metalhydrides such as sodium hydride, or alkali metal hydroxides such assodium hydroxide and potassium hydroxide, in an inert solvent attemperatures preferably between 25-120° C. Examples of solvent to beused include ethers such as THF, ethylene glycol dimethyl ether,tert-butylmethyl ether, and 1,4-dioxane, aromatic hydrocarbons such astoluene and xylene, nitriles such as acetonitrile or polar aproticsolvents such as N,N-dimethylformamide, N,N-dimethylacetamide,N-methyl-2-pyrrolidone or dimethyl sulfoxide. Examples of salts of thecompound of formula VIII include compounds of the formula VIIIa

R₁—S-M  (VIIIa),

wherein R₁ is as defined above and wherein M is, for example, sodium orpotassium.

Compounds of formula VII, wherein R₈, G₁, G₂, G₃, G₄, and G₅ are asdefined above, and wherein Q_(a) is a radical selected from the groupconsisting of formula Q_(1a) to Q_(2a) described above,

may be prepared by reacting an amidine compound of formula II, or a saltthereof (such as a hydrohalide salt, preferably a hydrochloride or ahydrobromide salt, or any other equivalent salt), wherein R₈, G₁, G₂,G₃, G₄, and G₅ are as defined above, with a hydrazide compound offormula IIIa, or a salt thereof, wherein Q_(a) is a radical selectedfrom the group consisting of formula Q_(1a) to Q_(2a) described above,optionally in presence of a base such as alkali metal carbonates, forexample sodium carbonate or potassium carbonate, in a solvent such asmethanol, ethanol, isopropanol, acetonitrile, N,N-dimethylformamide orN,N-dimethyl-acetamide, at temperatures between 0 and 200° C.,preferably between 50 and 150° C., optionally under microwaveirradiation. Such a process may be carried out in analogy to, forexample, G. Bonanomi et al., Chem Med Chem 2010, 5, 705-715. Thecompounds of formula II may be reacted with any configuration (E or Z,or any mixture thereof) on the carbon-nitrogen double bond.

Compounds of formula IIIa, or a salt thereof, wherein Q_(a) is asdefined above, may be prepared in analogy to processes described abovein the context of the preparation of compounds of the formula III.

Alternatively, compounds of formula I, wherein Q, R₈, G₁, G₂, G₃, G₄,and G₅ are as defined in formula I above,

can be prepared by reacting a compound of formula (X), wherein Q and R₈are as defined above, and wherein L_(G) is a halogen, preferably bromineor iodine, or a pseudohalogen such as C₁₋₄haloalkyl-sulfonate,especially triflate, with a compound of formula XI, wherein G₁, G₂, G₃,G₄ and G₅ are as defined above, and wherein R″ is for example hydrogen(in that case the compound of the formula XI is a boronic acid) orC₁-C₄alkyl (boronic ester), by means of a transition metal-catalyzedreaction. Indeed, the boronic acid of the formula XI, or a suitable saltor ester thereof, will react with a compound of the formula (X) underpalladium- or nickel-catalyzed conditions, such as for example theSuzuki-Miyaura conditions. Such cross coupling reactions are carried outin the presence of a base, such as sodium, potassium or cesiumcarbonate, in an inert solvent, such as tetrahydrofuran,N,N-dimethylformamide, dioxane or 1,2-dimethoxyethane, or such as1,2-dimethoxyethane-water mixtures, at temperatures between 25-200° C.,preferably 50-150° C., optionally under microwave irradiation. A varietyof metals, catalysts and ligands may be used in this reaction type, suchas for example[1,1-bis(diphenylphosphino)ferrocene]dichloro-palladium(II)(PdCl₂(dppf)) or bis(triphenylphosphine) palladium(II) dichloride(PdCl₂(PPh₃)₂). Reaction conditions and catalytic systems for such atransformation have been described, for example, in WO08/071405.Alternative boron-based reagents of the formula type XI may includeboronic esters (also named boronate esters) derived from2,3-dimethyl-2,3-butanediol (XIa), 2,2-dimethyl-1,3-propanediol (XIb),and 1,3-propanediol (XIc), and salt analogues of XI, such asorganotrifluoroborates, for example potassium trifluoroborate salts(XId).

Compounds of formula (X)

wherein Q and R₈ are as defined under formula I above, and wherein L_(G)is a halogen, preferably iodine or bromine, are novel and especiallydeveloped for the preparation of the compounds of formula I of thisinvention. The compounds of formula (X) therefore constitute a furtherobject of the invention. The preferred substituent definitions for thecompounds of formula I are also valid for the compounds of formula (X).

Compound of formula (X), wherein Q and R₈ are as defined above, andwherein L_(G) is a halogen, preferably bromine or iodine,

may be prepared by reacting a compound of formula XII, wherein Q and R₈are as defined above, with a halogenation reagent such asN-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide(NIS), or alternatively chlorine, bromine or iodine. Such halogenationreactions are carried out in an inert solvent, such as chloroform,carbon tetrachloride, 1,2-dichloroethane, acetic acid, ethers,acetonitrile or N,N-dimethylformamide, at temperatures between 25-200°C., preferably 25-100° C., as described, for example, in Journal ofMedicinal Chemistry, 52(14), 4370-4379, 2009.

Compounds of formula XII

wherein Q and R₈ are as defined under formula I above, are novel andespecially developed for the preparation of the compounds of formula Iof this invention. The compounds of formula XII therefore constitute afurther object of the invention. The preferred substituent definitionsfor the compounds of formula I are also valid for the compounds offormula XII.

The subgroup of compounds of formula (X) or XII, wherein Q, R₈ and L_(G)are as defined above and wherein X is SO (sulfoxide) and/or SO₂(sulfone), may be obtained by means of an oxidation reaction of thecorresponding sulfide compounds of formula (X) or XII, wherein X is S(sulfide), involving reagents such as, for example,m-chloroperoxybenzoic acid (mCPBA), hydrogen peroxide, oxone, sodiumperiodate, sodium hypochlorite or tert-butyl hypochlorite amongst otheroxidants. The oxidation reaction is generally conducted in the presenceof a solvent. Examples of the solvent to be used in the reaction includealiphatic halogenated hydrocarbons such as dichloro-methane andchloroform; alcohols such as methanol and ethanol; acetic acid; water;and mixtures thereof. The amount of the oxidant to be used in thereaction is generally 1 to 3 moles, preferably 2 to 2.2 moles ofoxidant, relative to 1 mole of the sulfide compounds (X) or XII toproduce the sulfone compounds (X) or XII. Such oxidation reactions havealready been described above.

The subgroup of compounds of formula XII, wherein Q is Q₁ and X is S,and wherein R₈, R₁, R₇ and R are as defined above, defining compounds offormula XIIa,

may be prepared by reacting a compound of formula XIII, wherein R₈, R₇and R are as defined above, and wherein X₁₂ is a halogen (preferablyfluorine or chlorine), with a compound of formula VIII

R₁—SH  (VIII),

or a salt thereof, wherein R₁ is as defined in formula I, optionally inthe presence of a suitable base, such as alkali metal carbonates, forexample sodium carbonate and potassium carbonate, or alkali metalhydrides such as sodium hydride, or alkali metal hydroxides such assodium hydroxide and potassium hydroxide, in an inert solvent attemperatures preferably between 25-120° C. Examples of solvent to beused include ethers such as THF, ethylene glycol dimethyl ether,tert-butylmethyl ether, and 1,4-dioxane, aromatic hydrocarbons such astoluene and xylene, nitriles such as acetonitrile or polar aproticsolvents such as N,N-dimethylformamide, N,N-dimethylacetamide,N-methyl-2-pyrrolidone or dimethyl sulfoxide. Examples of salts of thecompound of formula VIII include compounds of the formula VIIIa

R₁—S-M  (VIIIa),

wherein R₁ is as defined above and wherein M is, for example, sodium orpotassium.

Compounds of formula XIII, wherein R₈, R₇ and R are as defined above,and wherein X₁₂ is a halogen (preferably fluorine or chlorine),

may be prepared by reacting a compound of formula XIV, or a tautomerthereof, wherein R₈, R₇ and R are as defined above, and wherein X₁₂ is ahalogen (preferably fluorine or chlorine), with an oxidant such asnitric acid, in the presence of water, optionally in the presence of aninert co-solvent, at temperatures preferably between 25-180° C. Such anoxidative desulfurization process of a 1,2,4-triazole thione compound ofthe formula XIV, which involves loss of sulfur dioxide (SO₂ gasevolution) from an intermediate sulfinic acid, is described, forexample, in J. M. Kane et al., J. Heterocyclic Chem. 1995, 32, 183-87.

Compounds of formula XIV, or a tautomer thereof, wherein R₈, R₇ and Rare as defined above, and wherein X₁₂ is a halogen (preferably fluorineor chlorine),

may be prepared by reacting a compound of formula XV, wherein R₈, R₇ andR are as defined above, and wherein X₁₂ is a halogen (preferablyfluorine or chlorine), in the presence of a base, such as sodium,potassium or cesium carbonate, sodium or potassium hydrogen carbonate,tripotassium phosphate, sodium or potassium hydroxide, in an inertsolvent, such as water, dioxane, methanol or ethanol, or mixturesthereof, at temperatures between 25-200° C., preferably 50-150° C.,optionally under microwave irradiation, as described, for example, inChem Med Chem, 8(6), 994-1001, 2013 and Farmaco, Edizione Scientifica,36(3), 181-96, 1981. Compounds of formula XIV may exist as differenttautomeric forms, or in mixtures thereof. Description in the literatureabout such thione-thiol tautomeric forms may be found, for example, inChem. Pharm. Bull. 1973, 21, 1342-1350.

Compounds of formula XV, wherein R₈, R₇ and R are as defined above, andwherein X₁₂ is a halogen (preferably fluorine or chlorine),

may be prepared by

i) activation of a compound of formula XVI, wherein X₁₂, R₇ and R are asdefined above, by methods known to those skilled in the art anddescribed in, for example, Tetrahedron, 2005, 61 (46), 10827-10852, toform an activated species XVIa, wherein X₁₂, R₇ and R are as definedabove and wherein X₀₀ is halogen, preferably chlorine. For example,compounds XVIa where X₀₀ is halogen, preferably chlorine, are formed bytreatment of XVI with, for example, oxallyl chloride (COCl)₂ or thionylchloride SOCl₂ in the presence of catalytic quantities ofN,N-dimethylformamide DMF in inert solvents such as methylene chlorideCH₂Cl₂ or tetrahydrofuran THF at temperatures between 20 to 100° C.,preferably 25° C. Alternatively, treatment of compounds of formula XVIwith, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC ordicyclohexyl carbodiimide DCC will generate an activated species XVIa,wherein X₀₀ is X₀₁ or X₀₂ respectively, in an inert solvent, such aspyridine or tetrahydrofuran THF, optionally in the presence of a base,such as triethylamine, at temperatures between 50-180° C.; followed by

ii) treatment of the activated species XVIa with a thiosemicarbazidecompound of formula XVII (or a salt thereof), wherein R₈ is as definedabove, optionally in the presence of a base, such as triethylamine orpyridine, in an inert solvents such as dichloromethane, tetrahydrofuran,dioxane or toluene, at temperatures between 0 and 50° C., to form thecompounds of formula XV, as described, for example, in J. Med. Chem.1994, 37, 125-132. Certain bases, such as pyridine and triethylamine,may be employed successfully as both base and solvent.

Alternatively, compounds of the formula XV, wherein X₁₂, R₈, R₇ and Rare as defined above, may be prepared by reacting a hydrazide compoundof formula XIX, wherein X₁₂, R₇ and R are as defined above, with anisothiocyanate reagent of the formula XXI, wherein R₈ is as definedabove, in an inert solvent, such as tetrahydrofuran, dioxane, methanol,ethanol, acetonitrile or N,N-dimethylformamide, at temperatures between25-200° C., preferably 50-150° C., optionally under microwaveirradiation, as described, for example, in J. Med. Chem. 1994, 37,125-132.

Compounds of the formula XIX, or a salt thereof, wherein X₁₂, R₇ and Rare as defined above, may be prepared by either the direct action ofhydrazine XX (or a salt thereof), possibly in form of a hydrate,preferably hydrazine monohydrate, on an ester derivative XVIb of thecompound of formula XVI, wherein X₁₂, R₇ and R are as defined above andwherein R₀₀ is C₁-C₄alkyl, preferably methyl or ethyl, at temperaturesbetween 20 and 150° C., optionally under microwave irradiation. Such aprocess description may be found, for example, in M. H. Klingele et al,Eur. J. Org. Chem. 2004, 3422-3434. Alternatively, treatment of theactivated species XVIa with hydrazine XX (or a salt thereof), possiblyin form of a hydrate, preferably hydrazine monohydrate, optionally inthe presence of a base, such as triethylamine or pyridine, in an inertsolvents such as dichloro-methane, tetrahydrofuran, dioxane or toluene,at temperatures between 0 and 50° C., will also form the compounds offormula XIX.

Esters of formula XVIb, wherein X₁₂, R₇ and R are as defined above andwherein R₀₀ is C₁-C₄alkyl, preferably methyl or ethyl, may be preparedby either the direct action of an alcohol R₀₀-0H of formula XVIII,wherein R₀₀ is C₁-C₄alkyl, on compounds of formula XVIa, wherein X₁₂, R₇and R are as defined above, or by means of an esterification reaction ofcompounds of formula XVI with an alcohol R₀₀—OH of formula XVIII,wherein R₀₀ is C₁-C₄alkyl, in the presence of a catalytic amount of anacid, such as hydrochloric acid HCl or sulfuric acid H₂SO₄, underrefluxing conditions. Both of these methods are well known to a personskilled in the art and precedented in the literature.

Compounds of formula XVI and XVIb, wherein X₁₂, R₇ and R are as definedabove and wherein R₀₀ is C₁-C₄alkyl, are known compounds or can beprepared by known methods, described in the literature. Reagents offormula XVII and XXI, wherein R₈ is as defined above, are knowncompounds or can be prepared by known methods, described in theliterature.

The reactants can be reacted in the presence of a base. Examples ofsuitable bases are alkali metal or alkaline earth metal hydroxides,alkali metal or alkaline earth metal hydrides, alkali metal or alkalineearth metal amides, alkali metal or alkaline earth metal alkoxides,alkali metal or alkaline earth metal acetates, alkali metal or alkalineearth metal carbonates, alkali metal or alkaline earth metaldialkylamides or alkali metal or alkaline earth metal alkylsilylamides,alkylamines, alkylenediamines, free or N-alkylated saturated orunsaturated cycloalkylamines, basic heterocycles, ammonium hydroxidesand carbocyclic amines. Examples which may be mentioned are sodiumhydroxide, sodium hydride, sodium amide, sodium methoxide, sodiumacetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide,potassium carbonate, potassium hydride, lithium diisopropylamide,potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine,diisopropylethylamine, triethylenediamine, cyclohexylamine,N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine,4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU).

The reactants can be reacted with each other as such, i.e. withoutadding a solvent or diluent. In most cases, however, it is advantageousto add an inert solvent or diluent or a mixture of these. If thereaction is carried out in the presence of a base, bases which areemployed in excess, such as triethylamine, pyridine, N-methylmorpholineor N,N-diethylaniline, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range fromapproximately −80° C. to approximately +140° C., preferably fromapproximately −30° C. to approximately +100° C., in many cases in therange between ambient temperature and approximately +80° C.

A compound of formula I can be converted in a manner known per se intoanother compound of formula I by replacing one or more substituents ofthe starting compound of formula I in the customary manner by (an)othersubstituent(s) according to the invention.

Depending on the choice of the reaction conditions and startingmaterials which are suitable in each case, it is possible, for example,in one reaction step only to replace one substituent by anothersubstituent according to the invention, or a plurality of substituentscan be replaced by other substituents according to the invention in thesame reaction step.

Salts of compounds of formula I can be prepared in a manner known perse. Thus, for example, acid addition salts of compounds of formula I areobtained by treatment with a suitable acid or a suitable ion exchangerreagent and salts with bases are obtained by treatment with a suitablebase or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in the customary mannerinto the free compounds I, acid addition salts, for example, bytreatment with a suitable basic compound or with a suitable ionexchanger reagent and salts with bases, for example, by treatment with asuitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula I can be converted in a manner known perse into other salts of compounds of formula I, acid addition salts, forexample, into other acid addition salts, for example by treatment of asalt of inorganic acid such as hydrochloride with a suitable metal saltsuch as a sodium, barium or silver salt, of an acid, for example withsilver acetate, in a suitable solvent in which an inorganic salt whichforms, for example silver chloride, is insoluble and thus precipitatesfrom the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds offormula I, which have salt-forming properties can be obtained in freeform or in the form of salts.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can be present inthe form of one of the isomers which are possible or as a mixture ofthese, for example in the form of pure isomers, such as antipodes and/ordiastereomers, or as isomer mixtures, such as enantiomer mixtures, forexample racemates, diastereomer mixtures or racemate mixtures, dependingon the number, absolute and relative configuration of asymmetric carbonatoms which occur in the molecule and/or depending on the configurationof non-aromatic double bonds which occur in the molecule; the inventionrelates to the pure isomers and also to all isomer mixtures which arepossible and is to be understood in each case in this sense hereinaboveand hereinbelow, even when stereochemical details are not mentionedspecifically in each case.

Diastereomer mixtures or racemate mixtures of compounds of formula I, infree form or in salt form, which can be obtained depending on whichstarting materials and procedures have been chosen can be separated in aknown manner into the pure diasteromers or racemates on the basis of thephysicochemical differences of the components, for example by fractionalcrystallization, distillation and/or chromatography.

Enantiomer mixtures, such as racemates, which can be obtained in asimilar manner can be resolved into the optical antipodes by knownmethods, for example by recrystallization from an optically activesolvent, by chromatography on chiral adsorbents, for examplehigh-performance liquid chromatography (HPLC) on acetyl cellulose, withthe aid of suitable microorganisms, by cleavage with specific,immobilized enzymes, via the formation of inclusion compounds, forexample using chiral crown ethers, where only one enantiomer iscomplexed, or by conversion into diastereomeric salts, for example byreacting a basic end-product racemate with an optically active acid,such as a carboxylic acid, for example camphor, tartaric or malic acid,or sulfonic acid, for example camphorsulfonic acid, and separating thediastereomer mixture which can be obtained in this manner, for exampleby fractional crystallization based on their differing solubilities, togive the diastereomers, from which the desired enantiomer can be setfree by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to theinvention not only by separating suitable isomer mixtures, but also bygenerally known methods of diastereoselective or enantioselectivesynthesis, for example by carrying out the process according to theinvention with starting materials of a suitable stereochemistry.

N-oxides can be prepared by reacting a compound of the formula I with asuitable oxidizing agent, for example the H₂O₂/urea adduct in thepresence of an acid anhydride, e.g. trifluoroacetic anhydride. Suchoxidations are known from the literature, for example from J. Med.Chem., 32 (12), 2561-73, 1989 or WO 00/15615.

It is advantageous to isolate or synthesize in each case thebiologically more effective isomer, for example enantiomer ordiastereomer, or isomer mixture, for example enantiomer mixture ordiastereomer mixture, if the individual components have a differentbiological activity.

The compounds of formula I and, where appropriate, the tautomersthereof, in each case in free form or in salt form, can, if appropriate,also be obtained in the form of hydrates and/or include other solvents,for example those which may have been used for the crystallization ofcompounds which are present in solid form.

The compounds according to the following Tables 1 to 6 below can beprepared according to the methods described above. The examples whichfollow are intended to illustrate the invention and show preferredcompounds of formula I.

Table 1: This table discloses the 102 compounds 1.001 to 1.102 of theformula I-1a:

wherein X₁ is S, and Ra₁, R₁₁, G₁, G₂, G₃, G₄ and G₅ are as definedbelow:

TABLE 1 Comp. No Ra₁ R₁₁ G₁ G₂ G₃ G₄ G₅ 1.001 H —CH₂CH₃ CH CH C(CF₃) CHCH 1.002 CF₃ —CH₂CH₃ CH CH C(CF₃) CH CH 1.003 H —CH₂CH₃ CH C(CF₃) CH CHCH 1.004 CF₃ —CH₂CH₃ CH C(CF₃) CH CH CH 1.005 H —CH₂CH₃ N C(CF₃) CH CHCH 1.006 CF₃ —CH₂CH₃ N C(CF₃) CH CH CH 1.007 H —CH₂CH₃ N CH C(CF₃) CH CH1.008 CF₃ —CH₂CH₃ N CH C(CF₃) CH CH 1.009 H —CH₂CH₃ N CH CH C(CF₃) CH1.010 CF₃ —CH₂CH₃ N CH CH C(CF₃) CH 1.011 H —CH₂CH₃ CH N C(CF₃) CH CH1.012 CF₃ —CH₂CH₃ CH N C(CF₃) CH CH 1.013 H —CH₂CH₃ CH N CH C(CF₃) CH1.014 CF₃ —CH₂CH₃ CH N CH C(CF₃) CH 1.015 H —CH₂CH₃ CH C(CF₃) N CH CH1.016 CF₃ —CH₂CH₃ CH C(CF₃) N CH CH 1.017 H —CH₃ CH CH C(CF₃) CH CH1.018 CF₃ —CH₃ CH CH C(CF₃) CH CH 1.019 OCF₃ —CH₂CH₃ CH CH C(CF₃) CH CH1.020 OCHF₂ —CH₂CH₃ CH CH C(CF₃) CH CH 1.021 CF₂CF₃ —CH₂CH₃ CH CH C(CF₃)CH CH 1.022 CF₃ —CH₂CH₃ CH CH C(CN) CH CH 1.023 H —CH₂CH₃ CH CH C(OCF₃)CH CH 1.024 CF₃ —CH₂CH₃ CH CH C(OCF₃) CH CH 1.025 CF₃ —CH₃ CH CH C(OCF₃)CH CH 1.026 H —CH₂CH₃ CH CH C(CF₂CF₃) CH CH 1.027 CF₃ —CH₂CH₃ CH CHC(CF₂CF₃) CH CH 1.028 CF₃ —CH₃ CH CH C(CF₂CF₃) CH CH 1.029 H —CH₃ CHC(CF₃) CH CH CH 1.030 CF₃ —CH₃ CH C(CF₃) CH CH CH 1.031 OCF₃ —CH₂CH₃ CHC(CF₃) CH CH CH 1.032 OCHF₂ —CH₂CH₃ CH C(CF₃) CH CH CH 1.033 CF₂CF₃—CH₂CH₃ CH C(CF₃) CH CH CH 1.034 CF₃ —CH₂CH₃ CH C(CN) CH CH CH 1.035 H—CH₂CH₃ CH C(OCF₃) CH CH CH 1.036 CF₃ —CH₂CH₃ CH C(OCF₃) CH CH CH 1.037CF₃ —CH₃ CH C(OCF₃) CH CH CH 1.038 H —CH₂CH₃ CH C(CF₂CF₃) CH CH CH 1.039CF₃ —CH₂CH₃ CH C(CF₂CF₃) CH CH CH 1.040 CF₃ —CH₃ CH C(CF₂CF₃) CH CH CH1.041 H —CH₃ N CH C(CF₃) CH CH 1.042 CF₃ —CH₃ N CH C(CF₃) CH CH 1.043OCF₃ —CH₂CH₃ N CH C(CF₃) CH CH 1.044 OCHF₂ —CH₂CH₃ N CH C(CF₃) CH CH1.045 CF₂CF₃ —CH₂CH₃ N CH C(CF₃) CH CH 1.046 CF₃ —CH₂CH₃ N CH C(CN) CHCH 1.047 H —CH₂CH₃ N CH C(OCF₃) CH CH 1.048 CF₃ —CH₂CH₃ N CH C(OCF₃) CHCH 1.049 CF₃ —CH₃ N CH C(OCF₃) CH CH 1.050 H —CH₂CH₃ N CH C(CF₂CF₃) CHCH 1.051 CF₃ —CH₂CH₃ N CH C(CF₂CF₃) CH CH 1.052 CF₃ —CH₃ N CH C(CF₂CF₃)CH CH 1.053 H —CH₃ N CH CH C(CF₃) CH 1.054 CF₃ —CH₃ N CH CH C(CF₃) CH1.055 OCF₃ —CH₂CH₃ N CH CH C(CF₃) CH 1.056 OCHF₂ —CH₂CH₃ N CH CH C(CF₃)CH 1.057 CF₂CF₃ —CH₂CH₃ N CH CH C(CF₃) CH 1.058 CF₃ —CH₂CH₃ N CH CHC(CN) CH 1.059 H —CH₂CH₃ N CH CH C(OCF₃) CH 1.060 CF₃ —CH₂CH₃ N CH CHC(OCF₃) CH 1.061 CF₃ —CH₃ N CH CH C(OCF₃) CH 1.062 H —CH₂CH₃ N CH CHC(CF₂CF₃) CH 1.063 CF₃ —CH₂CH₃ N CH CH C(CF₂CF₃) CH 1.064 CF₃ —CH₃ N CHCH C(CF₂CF₃) CH 1.065 H —CH₃ CH N C(CF₃) CH CH 1.066 CF₃ —CH₃ CH NC(CF₃) CH CH 1.067 OCF₃ —CH₂CH₃ CH N C(CF₃) CH CH 1.068 OCHF₂ —CH₂CH₃ CHN C(CF₃) CH CH 1.069 CF₂CF₃ —CH₂CH₃ CH N C(CF₃) CH CH 1.070 CF₃ —CH₂CH₃CH N C(CN) CH CH 1.071 H —CH₂CH₃ CH N C(OCF₃) CH CH 1.072 CF₃ —CH₂CH₃ CHN C(OCF₃) CH CH 1.073 CF₃ —CH₃ CH N C(OCF₃) CH CH 1.074 H —CH₂CH₃ CH NC(CF₂CF₃) CH CH 1.075 CF₃ —CH₂CH₃ CH N C(CF₂CF₃) CH CH 1.076 CF₃ —CH₃ CHN C(CF₂CF₃) CH CH 1.077 H —CH₃ CH N CH C(CF₃) CH 1.078 CF₃ —CH₃ CH N CHC(CF₃) CH 1.079 OCF₃ —CH₂CH₃ CH N CH C(CF₃) CH 1.080 OCHF₂ —CH₂CH₃ CH NCH C(CF₃) CH 1.081 CF₂CF₃ —CH₂CH₃ CH N CH C(CF₃) CH 1.082 CF₃ —CH₂CH₃ CHN CH C(CN) CH 1.083 H —CH₂CH₃ CH N CH C(OCF₃) CH 1.084 CF₃ —CH₂CH₃ CH NCH C(OCF₃) CH 1.085 CF₃ —CH₃ CH N CH C(OCF₃) CH 1.086 H —CH₂CH₃ CH N CHC(CF₂CF₃) CH 1.087 CF₃ —CH₂CH₃ CH N CH C(CF₂CF₃) CH 1.088 CF₃ —CH₃ CH NCH C(CF₂CF₃) CH 1.089 CF₃ —CH₂CH₃ N —OCF2O— CH CH 1.090 CF₃ —CH₂CH₃ N CH—OCF2O— CH 1.091 CF₃ —CH₂CH₃ N CH CH —OCF2O— 1.092 CF₃ —CH₂CH₃ CH N—OCF2O— CH 1.093 CF₃ —CH₂CH₃ CH N CH —OCF2O— 1.094 CF₃ —CH₂CH₃ N C(CF₃)N CH CH 1.095 CF₃ —CH₂CH₃ N CH N C(CF₃) CH 1.096 CF₃ —CH₂CH₃ N C(CF₃) CHN CH 1.097 CF₃ —CH₂CH₃ N CH C(CF₃) N CH 1.098 CF₃ —CH₂CH₃ N C(CF₃) CH CHN 1.099 CF₃ —CH₂CH₃ N CH C(CF₃) CH N 1.100 CF₃ —CH₂CH₃ N N C(CF₃) CH CH1.101 CF₃ —CH₂CH₃ N N CH C(CF₃) CH 1.102 CF₃ —CH₂CH₃ CH N C(CF₃) N CH

and the N-oxides of the compounds of Table 1.

Table 2: This table discloses the 102 compounds 2.001 to 2.102 of theformula I-1a, wherein X₁ is SO, and Ra₁, R₁₁, G₁, G₂, G₃, G₄ and G₅ areas defined in Table 1.

Table 3: This table discloses the 102 compounds 3.001 to 3.102 of theformula I-1a, wherein X₁ is SO₂, and Ra₁, R₁₁, G₁, G₂, G₃, G₄ and G₅ areas defined in Table 1.

Table 4: This table discloses the 102 compounds 4.001 to 4.102 of theformula I-2a:

wherein X₂ is S, and Ra₂, R₁₂, G₁, G₂, G₃, G₄ and G₅ are as definedbelow:

TABLE 4 Comp. No Ra₂ R₁₂ G₁ G₂ G₃ G₄ G₅ 4.001 H —CH₂CH₃ CH CH C(CF₃) CHCH 4.002 CF₃ —CH₂CH₃ CH CH C(CF₃) CH CH 4.003 H —CH₂CH₃ CH C(CF₃) CH CHCH 4.004 CF₃ —CH₂CH₃ CH C(CF₃) CH CH CH 4.005 H —CH₂CH₃ N C(CF₃) CH CHCH 4.006 CF₃ —CH₂CH₃ N C(CF₃) CH CH CH 4.007 H —CH₂CH₃ N CH C(CF₃) CH CH4.008 CF₃ —CH₂CH₃ N CH C(CF₃) CH CH 4.009 H —CH₂CH₃ N CH CH C(CF₃) CH4.010 CF₃ —CH₂CH₃ N CH CH C(CF₃) CH 4.011 H —CH₂CH₃ CH N C(CF₃) CH CH4.012 CF₃ —CH₂CH₃ CH N C(CF₃) CH CH 4.013 H —CH₂CH₃ CH N CH C(CF₃) CH4.014 CF₃ —CH₂CH₃ CH N CH C(CF₃) CH 4.015 H —CH₂CH₃ CH C(CF₃) N CH CH4.016 CF₃ —CH₂CH₃ CH C(CF₃) N CH CH 4.017 H —CH₃ CH CH C(CF₃) CH CH4.018 CF₃ —CH₃ CH CH C(CF₃) CH CH 4.019 OCF₃ —CH₂CH₃ CH CH C(CF₃) CH CH4.020 OCHF₂ —CH₂CH₃ CH CH C(CF₃) CH CH 4.021 CF₂CF₃ —CH₂CH₃ CH CH C(CF₃)CH CH 4.022 CF₃ —CH₂CH₃ CH CH C(CN) CH CH 4.023 H —CH₂CH₃ CH CH C(OCF₃)CH CH 4.024 CF₃ —CH₂CH₃ CH CH C(OCF₃) CH CH 4.025 CF₃ —CH₃ CH CH C(OCF₃)CH CH 4.026 H —CH₂CH₃ CH CH C(CF₂CF₃) CH CH 4.027 CF₃ —CH₂CH₃ CH CHC(CF₂CF₃) CH CH 4.028 CF₃ —CH₃ CH CH C(CF₂CF₃) CH CH 4.029 H —CH₃ CHC(CF₃) CH CH CH 4.030 CF₃ —CH₃ CH C(CF₃) CH CH CH 4.031 OCF₃ —CH₂CH₃ CHC(CF₃) CH CH CH 4.032 OCHF₂ —CH₂CH₃ CH C(CF₃) CH CH CH 4.033 CF₂CF₃—CH₂CH₃ CH C(CF₃) CH CH CH 4.034 CF₃ —CH₂CH₃ CH C(CN) CH CH CH 4.035 H—CH₂CH₃ CH C(OCF₃) CH CH CH 4.036 CF₃ —CH₂CH₃ CH C(OCF₃) CH CH CH 4.037CF₃ —CH₃ CH C(OCF₃) CH CH CH 4.038 H —CH₂CH₃ CH C(CF₂CF₃) CH CH CH 4.039CF₃ —CH₂CH₃ CH C(CF₂CF₃) CH CH CH 4.040 CF₃ —CH₃ CH C(CF₂CF₃) CH CH CH4.041 H —CH₃ N CH C(CF₃) CH CH 4.042 CF₃ —CH₃ N CH C(CF₃) CH CH 4.043OCF₃ —CH₂CH₃ N CH C(CF₃) CH CH 4.044 OCHF₂ —CH₂CH₃ N CH C(CF₃) CH CH4.045 CF₂CF₃ —CH₂CH₃ N CH C(CF₃) CH CH 4.046 CF₃ —CH₂CH₃ N CH C(CN) CHCH 4.047 H —CH₂CH₃ N CH C(OCF₃) CH CH 4.048 CF₃ —CH₂CH₃ N CH C(OCF₃) CHCH 4.049 CF₃ —CH₃ N CH C(OCF₃) CH CH 4.050 H —CH₂CH₃ N CH C(CF₂CF₃) CHCH 4.051 CF₃ —CH₂CH₃ N CH C(CF₂CF₃) CH CH 4.052 CF₃ —CH₃ N CH C(CF₂CF₃)CH CH 4.053 H —CH₃ N CH CH C(CF₃) CH 4.054 CF₃ —CH₃ N CH CH C(CF₃) CH4.055 OCF₃ —CH₂CH₃ N CH CH C(CF₃) CH 4.056 OCHF₂ —CH₂CH₃ N CH CH C(CF₃)CH 4.057 CF₂CF₃ —CH₂CH₃ N CH CH C(CF₃) CH 4.058 CF₃ —CH₂CH₃ N CH CHC(CN) CH 4.059 H —CH₂CH₃ N CH CH C(OCF₃) CH 4.060 CF₃ —CH₂CH₃ N CH CHC(OCF₃) CH 4.061 CF₃ —CH₃ N CH CH C(OCF₃) CH 4.062 H —CH₂CH₃ N CH CHC(CF₂CF₃) CH 4.063 CF₃ —CH₂CH₃ N CH CH C(CF₂CF₃) CH 4.064 CF₃ —CH₃ N CHCH C(CF₂CF₃) CH 4.065 H —CH₃ CH N C(CF₃) CH CH 4.066 CF₃ —CH₃ CH NC(CF₃) CH CH 4.067 OCF₃ —CH₂CH₃ CH N C(CF₃) CH CH 4.068 OCHF₂ —CH₂CH₃ CHN C(CF₃) CH CH 4.069 CF₂CF₃ —CH₂CH₃ CH N C(CF₃) CH CH 4.070 CF₃ —CH₂CH₃CH N C(CN) CH CH 4.071 H —CH₂CH₃ CH N C(OCF₃) CH CH 4.072 CF₃ —CH₂CH₃ CHN C(OCF₃) CH CH 4.073 CF₃ —CH₃ CH N C(OCF₃) CH CH 4.074 H —CH₂CH₃ CH NC(CF₂CF₃) CH CH 4.075 CF₃ —CH₂CH₃ CH N C(CF₂CF₃) CH CH 4.076 CF₃ —CH₃ CHN C(CF₂CF₃) CH CH 4.077 H —CH₃ CH N CH C(CF₃) CH 4.078 CF₃ —CH₃ CH N CHC(CF₃) CH 4.079 OCF₃ —CH₂CH₃ CH N CH C(CF₃) CH 4.080 OCHF₂ —CH₂CH₃ CH NCH C(CF₃) CH 4.081 CF₂CF₃ —CH₂CH₃ CH N CH C(CF₃) CH 4.082 CF₃ —CH₂CH₃ CHN CH C(CN) CH 4.083 H —CH₂CH₃ CH N CH C(OCF₃) CH 4.084 CF₃ —CH₂CH₃ CH NCH C(OCF₃) CH 4.085 CF₃ —CH₃ CH N CH C(OCF₃) CH 4.086 H —CH₂CH₃ CH N CHC(CF₂CF₃) CH 4.087 CF₃ —CH₂CH₃ CH N CH C(CF₂CF₃) CH 4.088 CF₃ —CH₃ CH NCH C(CF₂CF₃) CH 4.089 CF₃ —CH₂CH₃ N —OCF2O— CH CH 4.090 CF₃ —CH₂CH₃ N CH—OCF2O— CH 4.091 CF₃ —CH₂CH₃ N CH CH —OCF2O— 4.092 CF₃ —CH₂CH₃ CH N—OCF2O— CH 4.093 CF₃ —CH₂CH₃ CH N CH —OCF2O— 4.094 CF₃ —CH₂CH₃ N C(CF₃)N CH CH 4.095 CF₃ —CH₂CH₃ N CH N C(CF₃) CH 4.096 CF₃ —CH₂CH₃ N C(CF₃) CHN CH 4.097 CF₃ —CH₂CH₃ N CH C(CF₃) N CH 4.098 CF₃ —CH₂CH₃ N C(CF₃) CH CHN 4.099 CF₃ —CH₂CH₃ N CH C(CF₃) CH N 4.100 CF₃ —CH₂CH₃ N N C(CF₃) CH CH4.101 CF₃ —CH₂CH₃ N N CH C(CF₃) CH 4.102 CF₃ —CH₂CH₃ CH N C(CF₃) N CH

and the N-oxides of the compounds of Table 4.

Table 5: This table discloses the 102 compounds 5.001 to 5.102 of theformula I-2a, wherein X₁ is SO, and Ra₂, R₁₂, G₁, G₂, G₃, G₄ and G₅ areas defined in Table 4.

Table 6: This table discloses the 102 compounds 6.001 to 6.102 of theformula I-2a, wherein X₁ is SO₂, and Ra₂, R₁₂, G₁, G₂, G₃, G₄ and G₅ areas defined in Table 4.

The compounds of formula I according to the invention are preventivelyand/or curatively valuable active ingredients in the field of pestcontrol, even at low rates of application, which have a very favorablebiocidal spectrum and are well tolerated by warm-blooded species, fishand plants. The active ingredients according to the invention actagainst all or individual developmental stages of normally sensitive,but also resistant, animal pests, such as insects or representatives ofthe order Acarina. The insecticidal or acaricidal activity of the activeingredients according to the invention can manifest itself directly, i.e. in destruction of the pests, which takes place either immediately oronly after some time has elapsed, for example during ecdysis, orindirectly, for example in a reduced oviposition and/or hatching rate, agood activity corresponding to a destruction rate (mortality) of atleast 50 to 60%.

Examples of the abovementioned animal pests are:

from the order Acarina, for example,

Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro,Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobiaspp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemusspp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp.,Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora,Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalusspp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp,Tarsonemus spp. and Tetranychus spp.;

from the order Anoplura, for example,

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.;

from the order Coleoptera, for example,

Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp.,Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis,Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp.,Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp.,Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp.,Heteronychus arator, Hypothenemus hampei, Lagria vilosa, LeptinotarsadecemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp,Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp.,Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophagaspp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatusaubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotrogaspp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebriospp., Tribolium spp. and Trogoderma spp.;

from the order Diptera, for example,

Aedes spp., Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibiohortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp.,Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp,Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyzatripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyzaspp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp.,Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp.,Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;

from the order Hemiptera, for example,

Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus,Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp.,Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma,Dichelops furcatus, Dysdercus spp., Edessa spp, Euchistus spp., Eurydemapulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus,Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic,Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans,Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp.,Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.,Thyanta spp, Triatoma spp., Vatiga illudens; Acyrthosium pisum, Adalgesspp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp,Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus,Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiellaspp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani,Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicorynebrassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp.,Chrysomphalus conidium, Chrysomphalus dictyospermi, Cicadella spp,Cofana spectra, Cryptomyzus spp, Cicadulina spp, Coccus hesperidum,Dalbulus maidis, Dialeurodes spp, Diaphorina citri, Diuraphis noxia,Dysaphis spp, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae,Hyalopterus spp, Hyperomyzus pallidus, Idioscopus clypealis, Jacobiascalybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphiserysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp, Metcalfapruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.,Neotoxoptera sp, Nephotettix spp., Nilaparvata spp., Nippolachnus piriMats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae,Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinusmaidis, Perkinsiella spp, Phorodon humuli, Phylloxera spp, Planococcusspp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelisseriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp.,Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera,Spissistilus festinus, Tarophagus Proserpina, Toxoptera spp,Trialeurodes spp, Tridiscus sporoboli, Trionymus spp, Trioza erytreae,Unaspis citri, Zygina flammigera, Zyginidia scutellaris;

from the order Hymenoptera, for example,

Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae,Gilpinia polytoma, Hoplo-camps spp., Lasius spp., Monomorium pharaonis,Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp.and Vespa spp.;

from the order Isoptera, for example,

Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermesspp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsisgeminate

from the order Lepidoptera, for example,

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrixthurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis,Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis,Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea,Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Estigmeneacrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella,Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedyanubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp,Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus,Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostegebifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestrabrassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp.,Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.,Panolis flammea, Papaipema nebris, Pectinophora gossypiela,Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaeaoperculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp.,Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp.,Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate,Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tutaabsolute, and Yponomeuta spp.;

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscusspp, and Schistocerca spp.;

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Siphonaptera, for example,

Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

from the order Thysanoptera, for example,

Calliothrips phaseoli, Frankliniella spp., Heliothrips spp,Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii,Sericothrips variabilis, Taeniothrips spp., Thrips spp;

from the order Thysanura, for example, Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

Suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; fruit, for example pomaceous fruit, stone fruit or soft fruit,such as apples, pears, plums, peaches, almonds, cherries or berries, forexample strawberries, raspberries or blackberries; leguminous crops,such as beans, lentils, peas or soya; oil crops, such as oilseed rape,mustard, poppies, olives, sunflowers, coconut, castor, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes or bellpeppers; Lauraceae, such as avocado, Cinnamonium or camphor; and alsotobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines,hops, the plantain family, latex plants and ornamentals.

The active ingredients according to the invention are especiallysuitable for controlling Aphis craccivora, Diabrotica balteata,Heliothis virescens, Myzus persicae, Plutella xylostella and Spodopteralittoralis in cotton, vegetable, maize, rice and soya crops. The activeingredients according to the invention are further especially suitablefor controlling Mamestra (preferably in vegetables), Cydia pomonella(preferably in apples), Empoasca (preferably in vegetables, vineyards),Leptinotarsa (preferably in potatos) and Chilo supressalis (preferablyin rice).

In a further aspect, the invention may also relate to a method ofcontrolling damage to plant and parts thereof by plant parasiticnematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasiticnematodes), especially plant parasitic nematodes such as root knotnematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, Meloidogyne arenaria and other Meloidogyne species;cyst-forming nematodes, Globodera rostochiensis and other Globoderaspecies; Heterodera avenae, Heterodera glycines, Heterodera schachtii,Heterodera trifolii, and other Heterodera species; Seed gall nematodes,Anguina species; Stem and foliar nematodes, Aphelenchoides species;Sting nematodes, Belonolaimus longicaudatus and other Belonolaimusspecies; Pine nematodes, Bursaphelenchus xylophilus and otherBursaphelenchus species; Ring nematodes, Criconema species, Criconemellaspecies, Criconemoides species, Mesocriconema species; Stem and bulbnematodes, Ditylenchus destructor, Ditylenchus dipsaci and otherDitylenchus species; Awl nematodes, Dolichodorus species; Spiralnematodes, Heliocotylenchus multicinctus and other Helicotylenchusspecies; Sheath and sheathoid nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species; Lance nematodes,Hoploaimus species; false rootknot nematodes, Nacobbus species; Needlenematodes, Longidorus elongatus and other Longidorus species; Pinnematodes, Pratylenchus species; Lesion nematodes, Pratylenchusneglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholussimilis and other Radopholus species; Reniform nematodes, Rotylenchusrobustus, Rotylenchus reniformis and other Rotylenchus species;Scutellonema species; Stubby root nematodes, Trichodorus primitivus andother Trichodorus species, Paratrichodorus species; Stunt nematodes,Tylenchorhynchus claytoni, Tylenchorhynchus dubius and otherTylenchorhynchus species; Citrus nematodes, Tylenchulus species; Daggernematodes, Xiphinema species; and other plant parasitic nematodespecies, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp.,Melinius spp., Punctodera spp., and Quinisulcius spp.

The compounds of the invention may also have activity against themolluscs. Examples of which include, for example, Ampullariidae; Arion(A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae(Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina;Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum);Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H.itala, H. obvia); Helicidae Helicigona arbustorum); Helicodiscus; Helix(H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L.maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M.sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising one or more selectively acting toxins,such as are known, for example, from toxin-producing bacteria,especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popilliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac,Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetativeinsecticidal proteins (Vip), e.g. Viol, Vip2, Vip3 or Vip3A; orinsecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for exampleVip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncatedtoxins and modified toxins. Hybrid toxins are produced recombinantly bya new combination of different domains of those proteins (see, forexample, WO 02/15701). Truncated toxins, for example a truncated Cry1Ab,are known. In the case of modified toxins, one or more amino acids ofthe naturally occurring toxin are replaced. In such amino acidreplacements, preferably non-naturally present protease recognitionsequences are inserted into the toxin, such as, for example, in the caseof Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3Atoxin (see WO 03/018810). Examples of such toxins or transgenic plantscapable of synthesising such toxins are disclosed, for example, inEP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cry1-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit and Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “crops” is to be understood as including also crop plants whichhave been so transformed by the use of recombinant DNA techniques thatthey are capable of synthesising antipathogenic substances having aselective action, such as, for example, the so-called“pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225).Examples of such antipathogenic substances and transgenic plants capableof synthesising such antipathogenic substances are known, for example,from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. The methods ofproducing such transgenic plants are generally known to the personskilled in the art and are described, for example, in the publicationsmentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Further areas of use of the compositions according to the invention arethe protection of stored goods and store rooms and the protection of rawmaterials, such as wood, textiles, floor coverings or buildings, andalso in the hygiene sector, especially the protection of humans,domestic animals and productive livestock against pests of the mentionedtype.

The present invention also provides a method for controlling pests (suchas mosquitoes and other disease vectors; see alsohttp://www.who.int/malaria/vector_control/irs/en/). In one embodiment,the method for controlling pests comprises applying the compositions ofthe invention to the target pests, to their locus or to a surface orsubstrate by brushing, rolling, spraying, spreading or dipping. By wayof example, an IRS (indoor residual spraying) application of a surfacesuch as a wall, ceiling or floor surface is contemplated by the methodof the invention. In another embodiment, it is contemplated to applysuch compositions to a substrate such as non-woven or a fabric materialin the form of (or which can be used in the manufacture of) netting,clothing, bedding, curtains and tents.

In one embodiment, the method for controlling such pests comprisesapplying a pesticidally effective amount of the compositions of theinvention to the target pests, to their locus, or to a surface orsubstrate so as to provide effective residual pesticidal activity on thesurface or substrate. Such application may be made by brushing, rolling,spraying, spreading or dipping the pesticidal composition of theinvention. By way of example, an IRS application of a surface such as awall, ceiling or floor surface is contemplated by the method of theinvention so as to provide effective residual pesticidal activity on thesurface. In another embodiment, it is contemplated to apply suchcompositions for residual control of pests on a substrate such as afabric material in the form of (or which can be used in the manufactureof) netting, clothing, bedding, curtains and tents.

Substrates including non-woven, fabrics or netting to be treated may bemade of natural fibres such as cotton, raffia, jute, flax, sisal,hessian, or wool, or synthetic fibres such as polyamide, polyester,polypropylene, polyacrylonitrile or the like. The polyesters areparticularly suitable. The methods of textile treatment are known, e.g.WO 2008/151984, WO 2003/034823, U.S. Pat. No. 5,631,072, WO 2005/64072,WO2006/128870, EP 1724392, WO2005113886 or WO 2007/090739.

Further areas of use of the compositions according to the invention arethe field of tree injection/trunk treatment for all ornamental trees aswell all sort of fruit and nut trees.

In the field of tree injection/trunk treatment, the compounds accordingto the present invention are especially suitable against wood-boringinsects from the order Lepidoptera as mentioned above and from the orderColeoptera, especially against woodborers listed in the following tablesA and B:

TABLE A Examples of exotic woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus planipennis AshCerambycidae Anoplura glabripennis Hardwoods Scolytidae Xylosandruscrassiusculus Hardwoods X. mutilatus Hardwoods Tomicus piniperdaConifers

TABLE B Examples of native woodborers of economic importance. FamilySpecies Host or Crop Infested Buprestidae Agrilus anxius Birch Agriluspolitus Willow, Maple Agrilus sayi Bayberry, Sweetfern Agrilusvittaticolllis Apple, Pear, Cranberry, Serviceberry, HawthornChrysobothris femorata Apple, Apricot, Beech, Boxelder, Cherry,Chestnut, Currant, Elm, Hawthorn, Hackberry, Hickory, Horsechestnut,Linden, Maple, Mountain-ash, Oak, Pecan, Pear, Peach, Persimmon, Plum,Poplar, Quince, Redbud, Serviceberry, Sycamore, Walnut, Willow Texaniacampestris Basswood, Beech, Maple, Oak, Sycamore, Willow, Yellow-poplarCerambycidae Goes pulverulentus Beech, Elm, Nuttall, Willow, Black oak,Cherrybark oak, Water oak, Sycamore Goes tigrinus Oak Neoclytusacuminatus Ash, Hickory, Oak, Walnut, Birch, Beech, Maple, Easternhophornbeam, Dogwood, Persimmon, Redbud, Holly, Hackberry, Black locust,Honeylocust, Yellow-poplar, Chestnut, Osage-orange, Sassafras, Lilac,Mountain-mahogany, Pear, Cherry, Plum, Peach, Apple, Elm, Basswood,Sweetgum Neoptychodes trilineatus Fig, Alder, Mulberry, Willow, Netleafhackberry Oberea ocellata Sumac, Apple, Peach, Plum, Pear, Currant,Blackberry Oberea tripunctata Dogwood, Viburnum, Elm, Sourwood,Blueberry, Rhododendron, Azalea, Laurel, Poplar, Willow, MulberryOncideres cingulata Hickory, Pecan, Persimmon, Elm, Sourwood, Basswood,Honeylocust, Dogwood, Eucalyptus, Oak, Hackberry, Maple, Fruit treesSaperda calcarata Poplar Strophiona nitens Chestnut, Oak, Hickory,Walnut, Beech, Maple Scolytidae Corthylus columbianus Maple, Oak,Yellow-poplar, Beech, Boxelder, Sycamore, Birch, Basswood, Chestnut, ElmDendroctonus frontalis Pine Dryocoetes betulae Birch, Sweetgum, Wildcherry, Beech, Pear Monarthrum fasciatum Oak, Maple, Birch, Chestnut,Sweetgum, Blackgum, Poplar, Hickory, Mimosa, Apple, Peach, PinePhloeotribus liminaris Peach, Cherry, Plum, Black cherry, Elm, Mulberry,Mountain-ash Pseudopityophthorus pruinosus Oak, American beech, Blackcherry, Chickasaw plum, Chestnut, Maple, Hickory, Hornbeam, HophornbeamSesiidae Paranthrene simulans Oak, American chestnut Sanninauroceriformis Persimmon Synanthedon exitiosa Peach, Plum, Nectarine,Cherry, Apricot, Almond, Black cherry Synanthedon pictipes Peach, Plum,Cherry, Beach, Black Cherry Synanthedon rubrofascia Tupelo Synanthedonscitula Dogwood, Pecan, Hickory, Oak, Chestnut, Beech, Birch, Blackcherry, Elm, Mountain-ash, Viburnum, Willow, Apple, Loquat, Ninebark,Bayberry Vitacea polistiformis Grape

The present invention may be also used to control any insect pests thatmay be present in turfgrass, including for example beetles,caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites,mole crickets, scales, mealybugs ticks, spittlebugs, southern chinchbugs and white grubs. The present invention may be used to controlinsect pests at various stages of their life cycle, including eggs,larvae, nymphs and adults.

In particular, the present invention may be used to control insect peststhat feed on the roots of turfgrass including white grubs (such asCyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp.(e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green Junebeetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica),Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Blackturfgrass ataenius, A. spretulus), Maladera spp. (e.g. Asiatic gardenbeetle, M. castanea) and Tomarus spp.), ground pearls (Margarodes spp.),mole crickets (tawny, southern, and short-winged; Scapteriscus spp.,Gryllotalpa africana) and leatherjackets (European crane fly, Tipulaspp.).

The present invention may also be used to control insect pests ofturfgrass that are thatch dwelling, including armyworms (such as fallarmyworm Spodoptera frugiperda, and common armyworm Pseudaletiaunipuncta), cutworms, billbugs (Sphenophorus spp., such as S. venatusverstitus and S. parvulus), and sod webworms (such as Crambus spp. andthe tropical sod webworm, Herpetogramma phaeopteralis).

The present invention may also be used to control insect pests ofturfgrass that live above the ground and feed on the turfgrass leaves,including chinch bugs (such as southern chinch bugs, Blissus insularis),Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug(Antonina graminis), two-lined spittlebug (Propsapia bicincta),leafhoppers, cutworms (Noctuidae family), and greenbugs. The presentinvention may also be used to control other pests of turfgrass such asred imported fire ants (Solenopsis invicta) that create ant mounds inturf.

In the hygiene sector, the compositions according to the invention areactive against ectoparasites such as hard ticks, soft ticks, mangemites, harvest mites, flies (biting and licking), parasitic fly larvae,lice, hair lice, bird lice and fleas.

Examples of such parasites are:

Of the order Anoplurida: Haematopinus spp., Linognathus spp., Pediculusspp. and Phtirus spp., Solenopotes spp.

Of the order Mallophagida: Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

Of the order Diptera and the suborders Nematocerina and Brachycerina,for example Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

Of the order Siphonapterida, for example Pulex spp., Ctenocephalidesspp., Xenopsylla spp., Ceratophyllus spp.

Of the order Heteropterida, for example Cimex spp., Triatoma spp.,Rhodnius spp., Panstrongylus spp.

Of the order Blattarida, for example Blatta orientalis, Periplanetaamericana, Blattelagermanica and Supella spp.

Of the subclass Acaria (Acarida) and the orders Meta- and Meso-stigmata,for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp.,Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,Pneumonyssus spp., Sternostoma spp. and Varroa spp.

Of the orders Actinedida (Prostigmata) and Acaridida (Astigmata), forexample Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobiaspp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp.,Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp.,Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. andLaminosioptes spp.

The compositions according to the invention are also suitable forprotecting against insect infestation in the case of materials such aswood, textiles, plastics, adhesives, glues, paints, paper and card,leather, floor coverings and buildings.

The compositions according to the invention can be used, for example,against the following pests: beetles such as Hylotrupes bajulus,Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum,Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobiumcarpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctuslinearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis,Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychuscapucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderusminutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas,Urocerus gigas taignus and Urocerus augur, and termites such asKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus, and bristletails such as Lepisma saccharina.

The invention therefore also relates to pesticidal compositions such asemulsifiable concentrates, suspension concentrates, microemulsions, oildispersibles, directly sprayable or dilutable solutions, spreadablepastes, dilute emulsions, soluble powders, dispersible powders, wettablepowders, dusts, granules or encapsulations in polymeric substances,which comprise—at least—one of the active ingredients according to theinvention and which are to be selected to suit the intended aims and theprevailing circumstances.

In these compositions, the active ingredient is employed in pure form, asolid active ingredient for example in a specific particle size, or,preferably, together with—at least—one of the auxiliaries conventionallyused in the art of formulation, such as extenders, for example solventsor solid carriers, or such as surface-active compounds (surfactants).

Examples of suitable solvents are: unhydrogenated or partiallyhydrogenated aromatic hydrocarbons, preferably the fractions C₈ to C₁₂of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes ortetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such asparaffins or cyclohexane, alcohols such as ethanol, propanol or butanol,glycols and their ethers and esters such as propylene glycol,dipropylene glycol ether, ethylene glycol or ethylene glycol monomethylether or ethylene glycol monoethyl ether, ketones, such ascyclohexanone, isophorone or diacetone alcohol, strongly polar solvents,such as N-methylpyrrolid-2-one, dimethyl sulfoxide orN,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils,such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil,and silicone oils.

Solid carriers which are used for example for dusts and dispersiblepowders are, as a rule, ground natural minerals such as calcite, talc,kaolin, montmorillonite or attapulgite. To improve the physicalproperties, it is also possible to add highly disperse silicas or highlydisperse absorbtive polymers. Suitable adsorptive carriers for granulesare porous types, such as pumice, brick grit, sepiolite or bentonite,and suitable non-sorptive carrier materials are calcite or sand. Inaddition, a large number of granulated materials of inorganic or organicnature can be used, in particular dolomite or comminuted plant residues.

Suitable surface-active compounds are, depending on the type of theactive ingredient to be formulated, non-ionic, cationic and/or anionicsurfactants or surfactant mixtures which have good emulsifying,dispersing and wetting properties. The surfactants mentioned below areonly to be considered as examples; a large number of further surfactantswhich are conventionally used in the art of formulation and suitableaccording to the invention are described in the relevant literature.Suitable non-ionic surfactants are, especially, polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, of saturated orunsaturated fatty acids or of alkyl phenols which may containapproximately 3 to approximately 30 glycol ether groups andapproximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatichydrocarbon radical or approximately 6 to approximately 18 carbon atomsin the alkyl moiety of the alkyl phenols. Also suitable arewater-soluble polyethylene oxide adducts with polypropylene glycol,ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having1 to approximately 10 carbon atoms in the alkyl chain and approximately20 to approximately 250 ethylene glycol ether groups and approximately10 to approximately 100 propylene glycol ether groups. Normally, theabovementioned compounds contain 1 to approximately 5 ethylene glycolunits per propylene glycol unit. Examples which may be mentioned arenonylphenoxypolyethoxyethanol, castor oil polyglycol ether,polypropylene glycol/polyethylene oxide adducts,tributylpheno-xypolyethoxyethanol, polyethylene glycol oroctylphenoxypolyethoxyethanol. Also suitable are fatty acid esters ofpolyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.The cationic surfactants are, especially, quarternary ammonium saltswhich generally have at least one alkyl radical of approximately 8 toapproximately 22 C atoms as substituents and as further substituents(unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzylradicals. The salts are preferably in the form of halides,methylsulfates or ethylsulfates. Examples are stearyltrimethylammoniumchloride and benzylbis(2-chloroethyl)ethylammonium bromide.

Examples of suitable anionic surfactants are water-soluble soaps orwater-soluble synthetic surface-active compounds. Examples of suitablesoaps are the alkali, alkaline earth or (unsubstituted or substituted)ammonium salts of fatty acids having approximately 10 to approximately22 C atoms, such as the sodium or potassium salts of oleic or stearicacid, or of natural fatty acid mixtures which are obtainable for examplefrom coconut or tall oil; mention must also be made of the fatty acidmethyl taurates. However, synthetic surfactants are used morefrequently, in particular fatty sulfonates, fatty sulfates, sulfonatedbenzimidazole derivatives or alkylaryl sulfonates. As a rule, the fattysulfonates and fatty sulfates are present as alkali, alkaline earth or(substituted or unsubstituted) ammonium salts and they generally have analkyl radical of approximately 8 to approximately 22 C atoms, alkyl alsoto be understood as including the alkyl moiety of acyl radicals;examples which may be mentioned are the sodium or calcium salts oflignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcoholsulfate mixture prepared from natural fatty acids. This group alsoincludes the salts of the sulfuric esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonyl groups and a fatty acid radical ofapproximately 8 to approximately 22 C atoms. Examples ofalkylarylsulfonates are the sodium, calcium or triethanolammonium saltsof decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of anaphthalenesulfonic acid/formaldehyde condensate. Also possible are,furthermore, suitable phosphates, such as salts of the phosphoric esterof a p-nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.

As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%,of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at leastone solid or liquid adjuvant, it being possible as a rule for 0 to 25%,especially 0.1 to 20%, of the composition to be surfactants (% in eachcase meaning percent by weight). Whereas concentrated compositions tendto be preferred for commercial goods, the end consumer as a rule usesdilute compositions which have substantially lower concentrations ofactive ingredient.

Typically, a pre-mix formulation for foliar application comprises 0.1 to99.9%, especially 1 to 95%, of the desired ingredients, and 99.9 to0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, forexample, a solvent such as water), where the auxiliaries can be asurfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on thepre-mix formulation.

Normally, a tank-mix formulation for seed treatment applicationcomprises 0.25 to 80%, especially 1 to 75%, of the desired ingredients,and 99.75 to 20%, especially 99 to 25%, of a solid or liquid auxiliaries(including, for example, a solvent such as water), where the auxiliariescan be a surfactant in an amount of 0 to 40%, especially 0.5 to 30%,based on the tank-mix formulation.

Typically, a pre-mix formulation for seed treatment applicationcomprises 0.5 to 99.9%, especially 1 to 95%, of the desired ingredients,and 99.5 to 0.1%, especially 99 to 5%, of a solid or liquid adjuvant(including, for example, a solvent such as water), where the auxiliariescan be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%,based on the pre-mix formulation.

Whereas commercial products will preferably be formulated asconcentrates (e.g., pre-mix composition (formulation)), the end userwill normally employ dilute formulations (e.g., tank mix composition).

Preferred seed treatment pre-mix formulations are aqueous suspensionconcentrates. The formulation can be applied to the seeds usingconventional treating techniques and machines, such as fluidized bedtechniques, the roller mill method, rotostatic seed treaters, and drumcoaters. Other methods, such as spouted beds may also be useful. Theseeds may be presized before coating. After coating, the seeds aretypically dried and then transferred to a sizing machine for sizing.Such procedures are known in the art.

In general, the pre-mix compositions of the invention contain 0.5 to99.9 especially 1 to 95, advantageously 1 to 50%, by mass of the desiredingredients, and 99.5 to 0.1, especially 99 to 5%, by mass of a solid orliquid adjuvant (including, for example, a solvent such as water), wherethe auxiliaries (or adjuvant) can be a surfactant in an amount of 0 to50, especially 0.5 to 40%, by mass based on the mass of the pre-mixformulation.

Examples of foliar formulation types for pre-mix compositions are:

GR: Granules

WP: wettable powders

WG: water dispersable granules (powders)

SG: water soluble granules

SL: soluble concentrates

EC: emulsifiable concentrate

EW: emulsions, oil in water

ME: micro-emulsion

SC: aqueous suspension concentrate

CS: aqueous capsule suspension

OD: oil-based suspension concentrate, and

SE: aqueous suspo-emulsion.

Whereas, examples of seed treatment formulation types for pre-mixcompositions are:

WS: wettable powders for seed treatment slurry

LS: solution for seed treatment

ES: emulsions for seed treatment

FS: suspension concentrate for seed treatment

WG: water dispersible granules, and

CS: aqueous capsule suspension.

Examples of formulation types suitable for tank-mix compositions aresolutions, dilute emulsions, suspensions, or a mixture thereof, anddusts.

Preferred compositions are composed in particular as follows (%=percentby weight):

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 5 to 20%

surfactant: 1 to 30%, preferably 10 to 20%

solvent: 5 to 98%, preferably 70 to 85%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 1%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%

water: 94 to 24%, preferably 88 to 30%

surfactant: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%

surfactant: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 99%, preferably 15 to 98%

Granulates:

active ingredient: 0.5 to 30%, preferably 3 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%

Preparatory Examples

“Mp” means melting point in ° C. Free radicals represent methyl groups.¹H NMR measurements were recorded on a Brucker 400 MHz spectrometer,chemical shifts are given in ppm relevant to a TMS standard. Spectrameasured in deuterated solvents as indicated. Common abbreviations:aq=aqueous, min=minute, h=hour, sat=saturated, R=retention time,mCPBA=meta-chloroperoxybenzoic acid, MeOH=methanol, EtOH=ethanol,NaHCO₃=sodium hydrogen carbonate, Na₂CO₃=sodium carbonate, HCl=hydrogenchloride, CH₂Cl₂=dichloromethane, Et₃N=triethylamine,DMF=N,N-dimethylformamide.

LCMS Methods:

Method 1:

SC_BASE, Apparatus: Agilent 1100 Bin. Pump: G1312A, degasser;autosampler, ColCom, DAD: Agilent G1315B, 220-320 nm, MSD: AgilentLC/MSD G6130B ESI, pos/neg 100-800; ELSD PL-ELS2100 gas flow 1.1 ml/min,gas temp: 50° C.; column: Waters XSelect™ C18, 30×2.1 mm, 3.5μ, Temp:25° C., Flow: 1 mL/min, Gradient: t₀=2% A, t_(1.6min)=98% A,t_(3min)=98% A, Posttime: 1.3 min, Eluent A: 95% acetonitrile+5% 10 mMammonium bicarbonate in water in acetonitrile, Eluent B: 10 mM ammoniumbicarbonate in water (pH=9.5).

Method 2:

AN_BASE, Apparatus: Agilent 1100 Bin. Pump: G1312A, degasser;autosampler, ColCom, DAD: Agilent G1315B, 220-320 nm, MSD: AgilentLC/MSD G6130B ESI, pos/neg 100-800; ELSD PL-ELS2100 gas flow 1.1 ml/min,gas temp: 50° C.; column: Waters XSelect™ C18, 50×2.1 mm, 3.5μ, Temp:25° C., Flow: 0.8 mL/min, Gradient: t₀=2% A, t_(3.5min)=98% A,t_(6min)=98% A, Posttime: 2 min, Eluent A: 95% acetonitrile+5% 10 mMammonium bicarbonate in water in acetonitrile, Eluent B: 10 mM ammoniumbicarbonate in water (pH=9.5).

Method 3:

Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQSingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive or negative ions, Capillary: 3.00 kV, Conerange: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH; gradient: 0 min 0% B, 100%A; 2.7-3.0 min 100% B; Flow (ml/min) 0.85.

Method 4:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII orZQ Single quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive or negative ions, Capillary: 3.00 kV, Conerange: 30-60 V, Extractor: 2.00 V, Source Temperature: 150° C.,Desolvation Temperature: 350° C., Cone Gas Flow: 0 L/Hr, Desolvation GasFlow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC fromWaters: Binary pump, heated column compartment and diode-array detector.Solvent degasser, binary pump, heated column compartment and diode-arraydetector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, Temp: 60° C.,DAD Wavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH; gradient: 10-100% B in 1.2min; Flow (ml/min) 0.85.

Method 5:

Spectra were recorded on an ACQUITY SQD Mass Spectrometer from Waters(Single quadrupole mass spectrometer). Ionisation method: Electrospray.Polarity: positive ions. Capillary (kV) 3.00, Cone (V) 20.00, Extractor(V) 3.00, Source Temperature (° C.) 150, Desolvation Temperature (° C.)400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700; Massrange: 100 to 800 Da; DAD Wavelength range (nm): 210 to 400.

Method Waters ACQUITY UPLC with the following HPLC gradient conditions

(Solvent A: Water/Methanol 9:1, 0.1% formic acid and Solvent B:Acetonitrile, 0.1% formic acid)

Time A B Flow rate (minutes) (%) (%) (ml/min) 0 100 0 0.75 2.5 0 1000.75 2.8 0 100 0.75 3.0 100 0 0.75

Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm;Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron;Temperature: 60° C.

Example P1: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethyl)pyridine(Compound P2) Step 1: Preparation of3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carbohydrazide

To a solution of3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carboxylic acid (4.4 g,17.51 mmol) in dichloromethane (70 ml) was added oxalyl chloride (7.25g, 57.1 mmol, 5.0 ml) followed by one drop of DMF and the mixture wasstirred at room temperature for 2 h. A red solution was obtained. Thereaction mixture was concentrated and coevaporated twice withdichloromethane. The red solid residue was dissolved in dichloromethane(50 ml) and added dropwise to a cooled (0° C.) solution of hydrazinemonohydrate (8.77 g, 175 mmol, 8.50 ml) in dichloromethane (50 ml) undernitrogen. After complete addition, the mixture was stirred for 30 min,the cooling bath was removed and stirring was continued for 90 moreminutes. A red suspension was obtained. The reaction mixture was dilutedwith dichloromethane and washed with sat. NaHCO₃ (aq), brine, dried oversodium sulfate and concentrated. The residue was purified over silica byflash column chromatography (0-10% methanol gradient in dichloromethane)to afford the title compound (2.58 g) as a solid. LCMS (method 1): 266(M+H)⁺, retention time 1.81 min. ¹H-NMR (CDCl₃, ppm) 1.44 (3H), 2.96(2H), 4.07 (2H), 7.83 (1H), 8.48 (1H), 8.94 (1H).

Step 2: Preparation ofN,N′-dimethyl-4-(trifluoromethyl)pyridine-2-carboxamidine HydrochlorideSalt

To a solution of 4-(trifluoromethyl)pyridine-2-carbonitrile (0.516 g,3.00 mmol) in methanol (4.5 ml) was added sodium methoxide (30 wt % inMeOH) (0.027 g, 0.150 mmol, 0.028 ml). The mixture was stirred at roomtemperature for 3 h. The solution was transferred into a reaction vial,methylamine (33 wt % in EtOH) (1.512 g, 16.07 mmol, 2.0 ml) was added,the vial was closed and the mixture was heated at 60° C. overnight.Hydrochloric acid (4M in dioxane) (3.00 mmol, 0.750 ml) was added andheating was continued at 90° C. for 2 h. The reaction mixture wasconcentrated. In a reaction vial, the residue was redissolved inmethylamine (33 wt % in EtOH) (7.56 g, 80 mmol, 10.00 ml), hydrochloricacid (4M in dioxane) (3.00 mmol, 0.750 ml) was added, the vial wascapped and the mixture was heated at 90° C. overnight. The reactionmixture was concentrated and the residue partitioned between diethylether and sat. Na₂CO₃ (aq). After washing and separation of the phases,the aqueous layer was extracted with ether two more times. The combinedorganic layers were dried over sodium sulfate and concentrated. Theresidue was purified over silica by flash column chromatography (0-100%B in A; A: CH₂Cl₂; B: CH₂Cl₂/MeOH/Et₃N, 9/1/0.1). The fractionscontaining product were combined and concentrated. The residue wasdissolved in methanol and hydrochloric acid in dioxane (4M, 2 ml) wasadded. The mixture was concentrated, coevaporated with methanol andtwice with diethyl ether to afford the title compound (484 mg) as asolid. LCMS (method 1): 218 (M+H)⁺, retention time 1.47 min. ¹H-NMR(DMSO-d6, ppm) 2.86 (3H), 3.06 (3H), 8.15 (1H), 8.29 (1H), 9.09 (1H),9.87 (1H), 10.23 (1H).

Step 3: Preparation of3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethyl)pyridine(Compound P1)

To a solution of3-ethylsulfanyl-5-(trifluoromethyl)pyridine-2-carbohydrazide (265 mg,1.00 mmol) and N,N′-dimethyl-4-(trifluoromethyl)pyridine-2-carboxamidinehydrochloride salt (254 mg, 1.00 mmol) in methanol (6.5 ml) was addedpotassium carbonate (138 mg, 1.00 mmol) and the mixture was heated atreflux temperature overnight. The reaction mixture was concentrated. Theresidue was partitioned between ethyl acetate and water. After washingand separation of the phases, the organic layer was dried over sodiumsulfate and concentrated. The residue was purified over silica by flashcolumn chromatography (5-40% ethyl acetate gradient in heptane) toafford the title compound (262 mg) as a solid, mp 113-114° C. LCMS(method 2): 434 (M+H)⁺, retention time 3.80 min. ¹H-NMR (CDCl₃, ppm)1.38 (3H), 3.02 (2H), 4.20 (3H), 7.60 (1H), 7.92 (1H), 8.71 (1H), 8.74(1H), 8.88 (1H).

Step 4: Preparation of3-ethylsulfonyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethyl)pyridine(Title Compound P2)

To a solution of3-ethylsulfanyl-2-[4-methyl-5-[4-(trifluoromethyl)-2-pyridyl]-1,2,4-triazol-3-yl]-5-(trifluoromethyl)pyridine(215 mg, 0.496 mmol) in dichloromethane (5 ml) was added mCPBA (70 wt %in water) (257 mg, 1.042 mmol, 70%) in one portion and mixture wasstirred at room temperature overnight. The reaction mixture was dilutedwith dichloromethane, washed with sat. aqueous sodium thiosulfatesolution/sat. NaHCO₃ (1/1), sat. NaHCO₃, dried over sodium sulfate andconcentrated. The residue was purified over silica by flash columnchromatography (5-40% ethyl acetate gradient in heptane). The fractionscontaining product were combined and concentrated. The product was againpurified over silica by flash column chromatography (0-2.5% methanolgradient in dichloromethane) to afford the title compound (183 mg) as asolid, mp 184-185° C. LCMS (method 2): 466 (M+H)⁺, retention time 3.76min. ¹H-NMR (CDCl₃, ppm) 1.41 (3H), 3.93 (2H), 4.12 (3H), 7.62 (1H),8.71 (1H), 8.77 (1H), 8.89 (1H), 9.25 (1H).

Example P2: Preparation of2-(5-bromo-4-methyl-1,2,4-triazol-3-yl)-3-ethylsulfonyl-5-(trifluoromethyl)pyridineStep 1: Preparation of1-[[3-chloro-5-(trifluoromethyl)pyridine-2-carbonyl]amino]-3-methyl-thiourea

To a solution of 1-amino-3-methyl-thiourea (1.94 g, 18.44 mmol) inpyridine (2.5 ml) and dichloromethane (35 ml) at 10° C. was added asolution of 3-chloro-5-(trifluoromethyl)pyridine-2-carbonyl chloride(5.0 g, 20.49 mmol) in dichloromethane (15 ml) dropewise over one hour.The reaction mixture was stirred overnight at room temperature, thenconcentrated under reduced pressure. The residue was treated with water(50 ml), the suspension filtered and the solid washed with cold water.The crude material was dissolved in ethyl acetate, dried over sodiumsulfate and concentrated to afford the title compound (3.4 g) as a paleyellow solid, mp 181-182° C. This material was used without furtherpurification. LCMS (method 3): 313/315 (M+H)⁺, retention time 0.83 min.¹H-NMR (methanol-d4, ppm) 3.05 (3H), 8.43 (1H), 8.91 (1H).

Step 2: Preparation of3-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-methyl-1H-1,2,4-triazole-5-thione

A stirred suspension of1-[[3-chloro-5-(trifluoromethyl)pyridine-2-carbonyl]amino]-3-methyl-thiourea(1.0 g, 3.20 mmol) in aqueous 2M sodium bicarbonate (20 ml) was slowlyheated to reflux. After refluxing overnight, the reaction mixture wascooled, filtered and the clear yellow filtrate carefully acidified bydropwise addition of concentrated hydrochloric acid at 0° C. Theresulting solid was collected by filtration, washed with cold water,dissolved in ethyl acetate, the solution dried over sodium sulfate andconcentrated to afford the title compound (720 mg) as a pale yellowsolid, mp 226-228° C. This material was used without furtherpurification. LCMS (method 3): 295/297 (M+H)⁺, retention time 1.11 min.¹H-NMR (DMSO-d6, ppm) 3.52 (3H), 8.79 (1H), 9.16 (1H), 14.31 (1H).

Step 3: Preparation of3-chloro-2-(4-methyl-1,2,4-triazol-3-yl)-5-(trifluoromethyl)pyridine

A suspension of3-[3-chloro-5-(trifluoromethyl)-2-pyridyl]-4-methyl-1H-1,2,4-triazole-5-thione(500 mg, 1.70 mmol) in a mixture of 65% nitric acid (2 ml) and water (15ml) was warmed gently (caution!). After a short induction period, gasevolution was observed. The reaction was completed by slowly increasingthe temperature and heating at reflux for one hour. The reaction mixturewas cooled to 10° C. and basified by addition of aqueous 30% sodiumhydroxide. The suspension was filtered and the solid washed with coldwater. The aqueous filtrate was extracted with dichloromethane (3×) andthe previously obtained solid dissolved in the separated organic layer.This dichloromethane layer was dried over sodium sulfate andconcentrated to afford the title compound (350 mg) as a solid, mp130-131.5° C. This material was used without further purification. LCMS(method 3): 263/265 (M+H)⁺, retention time 0.82 min. ¹H-NMR (CDCl₃, ppm)3.88 (3H), 8.17 (1H), 8.29 (1H), 8.88 (1H).

Step 4: Preparation of3-ethylsulfanyl-2-(4-methyl-1,2,4-triazol-3-yl)-5-(trifluoromethyl)pyridine

To a solution of3-chloro-2-(4-methyl-1,2,4-triazol-3-yl)-5-(trifluoromethyl)pyridine(25.0 g, 95.19 mmol) in dry N,N-dimethylformamide (200 ml) at 0-5° C.was added sodium ethanethiolate (18.9 g, 90%, 199.8 mmol) in fourportions and the mixture was stirred at 0-5° C. for 30 minutes, then atroom temperature for 3 hours. The solvent was removed under reducedpressure, the solid residue treated with water (250 ml), the suspensionfiltered and the solid washed with cold water (4×100 ml). The crudematerial was dissolved in dichloromethane, dried over sodium sulfate andconcentrated to afford the title compound (26.3 g) as a pale yellowsolid, mp 165-166° C. This material was used without furtherpurification. LCMS (method 3): 289 (M+H)⁺, retention time 1.08 min.¹H-NMR (CDCl₃, ppm) 1.40 (3H), 3.01 (2H), 3.94 (3H), 7.88 (1H), 8.25(1H), 8.66 (1H).

Step 5: Preparation of3-ethylsulfonyl-2-(4-methyl-1,2,4-triazol-3-yl)-5-(trifluoromethyl)pyridine

To a solution of3-ethylsulfanyl-2-(4-methyl-1,2,4-triazol-3-yl)-5-(trifluoromethyl)pyridine(24.0 g, 83.25 mmol) in dichloromethane (300 ml) at 10° C. was addedmCPBA (75 wt % in water) (40.22 g, 174.8 mmol, 75%) in six portions andthe mixture was stirred at room temperature overnight. The reactionmixture was filtered, the filtrate washed with an aqueous 10% sodiumthiosulfate solution (3×), then with sat. aqueous NaHCO₃ (4×) and brine,dried over sodium sulfate and concentrated to afford the title compound(25.5 g) as a white solid, mp 185-187° C. This material was used withoutfurther purification. LCMS (method 3): 321 (M+H)⁺, retention time 0.85min. ¹H-NMR (CDCl₃, ppm) 1.39 (3H), 3.75 (3H), 3.94 (2H), 8.28 (1H),8.76 (1H), 9.19 (1H).

Step 6: Preparation of2-(5-bromo-4-methyl-1,2,4-triazol-3-yl)-3-ethylsulfonyl-5-(trifluoromethyl)pyridine

To a solution of3-ethylsulfonyl-2-(4-methyl-1,2,4-triazol-3-yl)-5-(trifluoromethyl)pyridine(15.0 g, 46.8 mmol) in acetonitrile (250 ml) was added N-bromosuccinimide (20.84 g, 117.1 mmol) and the mixture was heated at refluxtemperature overnight. The reaction mixture was concentrated and theresidue diluted with dichloromethane, washed with saturated aqueoussodium bicarbonate, brine, dried over magnesium sulfate andconcentrated. The residue was purified over silica by flash columnchromatography (cyclohexane/ethyl acetate 3:1) to afford the titlecompound (15.5 g) as a solid, mp 172-173° C. LCMS (method 3): 399/401(M+H)⁺, retention time 1.11 min. ¹H-NMR (CDCl₃, ppm) 1.39 (3H), 3.67(3H), 3.89 (2H), 8.75 (1H), 9.20 (1H).

Example P3: Preparation of2-(5-bromo-4-methyl-1,2,4-triazol-3-yl)-3-ethylsulfanyl-5-(trifluoromethyl)pyridine

Obtained from3-ethylsulfanyl-2-(4-methyl-1,2,4-triazol-3-yl)-5-(trifluoromethyl)pyridine(100 mg, 0.347 mmol) and N-bromo succinimide (61 mg, 0.343 mmol) incarbon tetrachloride (0.3 ml) according to procedure Example P2, step 6.The mixture was stirred at reflux temperature for 30 minutes. Combiflashpurification afforded the title compound (66 mg) as a solid. LCMS(method 4): 367/369 (M+H)⁺, retention time 0.91 min. ¹H-NMR (CDCl₃, ppm)1.39 (3H), 3.01 (2H), 3.85 (3H), 7.89 (1H), 8.67 (1H).

Example P4: Preparation of2-[5-[3,4-bis(trifluoromethyl)phenyl]-4-methyl-1,2,4-triazol-3-yl]-3-ethylsulfonyl-5-(trifluoromethyl)pyridine(Compound P61)

In a microwave vial, a mixture of2-(5-bromo-4-methyl-1,2,4-triazol-3-yl)-3-ethylsulfonyl-5-(trifluoromethyl)pyridine(250 mg, 0.63 mmol), [3,4-bis(trifluoromethyl)phenyl]boronic acid (404mg, 1.57 mmol) in 1,2-dimethoxyethane (3 ml) and aqueous 2M sodiumcarbonate (0.94 ml, 1.88 mmol) was flushed with argon for 5 minutes.Bis(triphenylphosphine)palladium(II) dichloride (4.4 mg, 0.0063 mmol)was added, the vial was closed and heated in the microwave at 110° C.for 2.5 hours. The reaction mixture was diluted with dichloromethane andwashed with water, brine, dried over sodium sulfate and concentrated.The residue was purified over silica by flash column chromatography(cyclohexane/ethyl acetate 3:1) to afford the title compound P61 (145mg) as a solid, mp 91-93° C. LCMS (method 3): 533 (M+H)⁺, retention time1.78 min. ¹H-NMR (CDCl₃, ppm) 1.43 (3H), 3.77 (3H), 3.96 (2H), 8.08(1H), 8.13 (1H), 8.33 (1H), 8.79 (1H), 9.25 (1H).

TABLE P1 Examples of compounds of formula (I) Compound Melting No.Structures Point MS/NMR P1 

113-114° C. LCMS (method 2): 434 (M + H)⁺ R_(t) = 3.80 min P2 

184-185° C. LCMS (method 2): 466 (M + H)⁺ R_(t) = 3.76 min P3  118-119°C. LCMS (method 2): 434 (M + H)⁺ R_(t) = 3.56 min ¹H-NMR (CDCl₃, ppm)1.42 (3H), 3.05 (2H), 3.93 (3H), 7.93 (1H), 8.42 (1H), 8.72 (1H), 9.06(1H), 9.20 (1H). P4  192-194° C. LCMS (method 2): 466 (M + H)⁺ R_(t) =3.38 min ¹H-NMR (CDCl₃, ppm) 1.43 (3H), 3.93 (3H), 3.97 (2H), 8.44 (1H),8.79 (1H), 9.08 (1H), 9.22 (1H), 9.25 (1H). LCMS Compound R_(t) [M + H]⁺Mp No. Structures (min) (measured) Method (° C.) P5 

3.63 465 2 155-156 P6 

3.55 466 2 146-147 P7 

3.62 465 2 solid P8 

3.46 466 2 150-151 P9 

3.98 434 2 160-161 P10

3.73 466 2 167-169 P11

1.34 397 5 P12

1.78 533 5 P13

1.37 433 5 P14

1.37 415 5 P15

1.53 449 5 P16

1.67 464 5 P17

1.37 415 5 P18

1.41 433 5 P19

1.58 483 5 P20

1.62 481 5 P21

1.83 565 5 P22

1.54 449 5 P23

1.37 423 5 P24

1.64 480 5 P25

1.67 499 5 P26

1.54 449 5 P27

1.48 465 5 P28

1.50 431 5 P29

1.45 433 5 P30

1.57 477 5 P31

1.48 449 5 P32

1.39 415 5 P33

1.62 481 5 P34

1.30 422 5 P35

1.30 422 5 P36

1.44 431 5 P37

1.15 423 5 P38

1.20 423 5 P39

1.52 469 5 P40

1.02 399 5 P41

1.01 398 5 P42

1.04 398 5 P43

1.28 431 5 P44

1.22 416 5 P45

1.64 499 5 P46

1.64 464 5 P47

1.60 464 5 P48

1.70 499 5 P49

4.11 434 2 140-141 P50

3.77 466 2 199-200 P51

3.50 440 2 193-195 P52

3.56 440 2 196-198 P53

3.65 447 2 169-170 P54

1.02 433 4 170-171 P55

0.92 465 4 245-246 P56

1.57 477 3 160-161 P57

0.94 432 4  96-101 P58

0.88 464 4 162-163 P59

1.11 433 4 90-91 P60

1.00 465 4 165-166 P61

1.78 533 3 91-93 P62

1.40 467 3 233-235 P63

1.80 500/502 3 208-210 P64

1.88 448 3 gum P65

1.74 480 3 184-186 P66

0.96 464 4 189-192 P67 1.14 484 4 97-99 P68 1.07 516 4 170-172 P69

1.21 398 3 P70

1.72 420 3 131-133 P71

1.57 452 3 208-209 P72

1.82 492 3 179-180 P73

1.81 516 3 P74

0.92 397 4 P75

1.26 397 3 88-90 P76

1.94 460 3 133-135 P77

1.18 484 4 P78

1.06 365 4

Formulation Examples (%=Percent by Weight)

Example F1: Emulsion Concentrates

a) b) c) Active ingredient 25% 40% 50% Calcium dodecylbenzenesulfonate 5%  8%  6% Castor oil polyethylene  5% — — glycol ether (36 mol of EO)Tributylphenoxypolyethylene — 12%  4% glycol ether (30 mol of EO)Cyclohexanone — 15% 20% Xylene mixture 65% 25% 20%

Emulsions of any desired concentration can be prepared from suchconcentrates by dilution with water.

Example F2: Solutions

a) b) c) d) Active ingredient 80% 10% 5% 95% Ethylene glycol monomethyl20% — — — ether Polyethylene glycol — 70% — — MW 400N-Methylpyrrolid-2-one — 20% — — Epoxidized coconut oil — — 1%  5%Petroleum ether — — 94%  — (boiling range: 160-190°)

The solutions are suitable for use in the form of microdrops.

Example F3: Granules

a) b) c) d) Active ingredient 5% 10%  8% 21% Kaolin 94%  — 79% 54%Highly disperse silica 1% — 13%  7% Attapulgite — 90% — 18%

The active ingredient is dissolved in dichloromethane, the solution issprayed onto the carrier(s), and the solvent is subsequently evaporatedin vacuo.

Example F4: Dusts

a) b) Active ingredient 2% 5% Highly disperse silica 1% 5% Talc 97%  —Kaolin — 90% 

Ready-to-use dusts are obtained by intimately mixing the carriers andthe active ingredient.

Example F5: Wettable Powders

a) b) c) Active ingredient 25%  50% 75% Sodium lignosulfonate 5%  5% —Sodium lauryl sulfate 3% —  5% Sodium diisobutyl- —  6% 10%naphthalenesulfonate Octylphenoxypolyethylene —  2% — glycol ether (7-8mol of EO) Highly disperse silica 5% 10% 10% Kaolin 62%  27% —

The active ingredient is mixed with the additives and the mixture isground thoroughly in a suitable mill. This gives wettable powders, whichcan be diluted with water to give suspensions of any desiredconcentration.

Example F6: Extruder Granules

Active ingredient 10% Sodium lignosulfonate  2% Carboxymethylcellulose 1% Kaolin 87%

The active ingredient is mixed with the additives, and the mixture isground, moistened with water, extruded, granulated and dried in a streamof air.

Example F7: Coated Granules

Active ingredient 3% Polyethylene glycol (MW 200) 3% Kaolin 94% 

In a mixer, the finely ground active ingredient is applied uniformLy tothe kaolin, which has been moistened with the polyethylene glycol. Thisgives dust-free coated granules.

Example F8: Suspension Concentrate

Active ingredient 40% Ethylene glycol 10% Nonylphenoxypolyethyleneglycol ether (15 mol of EO)  6% Sodium lignosulfonate 10%Carboxymethylcellulose  1% 37% aqueous formaldehyde solution 0.2% Silicone oil (75% aqueous emulsion) 0.8%  Water 32%

The finely ground active ingredient is mixed intimately with theadditives. Suspensions of any desired concentration can be prepared fromthe thus resulting suspension concentrate by dilution with water.

Example F9: Powders for Dry Seed Treatment

a) b) c) active ingredient 25% 50% 75% light mineral oil  5%  5%  5%highly dispersed silicic acid  5%  5% — Kaolin 65% 40% — Talcum — — 20%

The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording powders that can beused directly for seed treatment.

Example F10: Emulsifiable Concentrate

active ingredient 10% octylphenol polyethylene glycol ether  3% (4-5 molof ethylene oxide) calcium dodecylbenzenesulfonate  3% castor oilpolyglycol ether (35 mol of ethylene oxide)  4% Cyclohexanone 30% xylenemixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Example F11: Flowable Concentrate for Seed Treatment

active ingredients 40%  propylene glycol 5% copolymer butanol PO/EO 2%Tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (inthe form of a 20% solution in 0.5%  water) monoazo-pigment calcium salt5% Silicone oil (in the form of a 75% emulsion in water) 0.2%  Water45.3%  

The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

The activity of the compositions according to the invention can bebroadened considerably, and adapted to prevailing circumstances, byadding other insecticidally, acaricidally and/or fungicidally activeingredients. The mixtures of the compounds of formula I with otherinsecticidally, acaricidally and/or fungicidally active ingredients mayalso have further surprising advantages which can also be described, ina wider sense, as synergistic activity. For example, better tolerance byplants, reduced phytotoxicity, insects can be controlled in theirdifferent development stages or better behaviour during theirproduction, for example during grinding or mixing, during their storageor during their use. Suitable additions to active ingredients here are,for example, representatives of the following classes of activeingredients: organophosphorus compounds, nitrophenol derivatives,thioureas, juvenile hormones, formamidines, benzophenone derivatives,ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinatedhydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides,neonicotinoids and Bacillus thuringiensis preparations.

The following mixtures of the compounds of formula I with activeingredients are preferred (the abbreviation “TX” means “one compoundselected from the group consisting of the compounds described in Tables1 to 6 of the present invention”):

an adjuvant selected from the group of substances consisting ofpetroleum oils (alternative name) (628)+TX,

an acaricide selected from the group of substances consisting of1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX,2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name)(1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name)(1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX,abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin(202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amidothioate(872)+TX, amiton (875)+TX, amiton hydrogen oxalate (875)+TX, amitraz(24)+TX, aramite (881)+TX, arsenous oxide (882)+TX, AVI 382 (compoundcode)+TX, AZ 60541 (compound code)+TX, azinphos-ethyl (44)+TX,azinphos-methyl (45)+TX, azobenzene (IUPAC name) (888)+TX, azocyclotin(46)+TX, azothoate (889)+TX, benomyl (62)+TX, benoxafos (alternativename) [CCN]+TX, benzoximate (71)+TX, benzyl benzoate (IUPAC name)[CCN]+TX, bifenazate (74)+TX, bifenthrin (76)+TX, binapacryl (907)+TX,brofenvalerate (alternative name)+TX, bromocyclen (918)+TX, bromophos(920)+TX, bromophos-ethyl (921)+TX, bromopropylate (94)+TX, buprofezin(99)+TX, butocarboxim (103)+TX, butoxycarboxim (104)+TX, butylpyridaben(alternative name)+TX, calcium polysulfide (IUPAC name) (111)+TX,camphechlor (941)+TX, carbanolate (943)+TX, carbaryl (115)+TX,carbofuran (118)+TX, carbophenothion (947)+TX, CGA 50′439 (developmentcode) (125)+TX, chinomethionat (126)+TX, chlorbenside (959)+TX,chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorfenapyr (130)+TX, chlorfenethol (968)+TX, chlorfenson (970)+TX,chlorfensulfide (971)+TX, chlorfenvinphos (131)+TX, chlorobenzilate(975)+TX, chloromebuform (977)+TX, chloromethiuron (978)+TX,chloropropylate (983)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl(146)+TX, chlorthiophos (994)+TX, cinerin I (696)+TX, cinerin II(696)+TX, cinerins (696)+TX, clofentezine (158)+TX, closantel(alternative name) [CCN]+TX, coumaphos (174)+TX, crotamiton (alternativename) [CCN]+TX, crotoxyphos (1010)+TX, cufraneb (1013)+TX, cyanthoate(1020)+TX, cyflumetofen (CAS Reg. No.: 400882-07-7)+TX, cyhalothrin(196)+TX, cyhexatin (199)+TX, cypermethrin (201)+TX, DCPM (1032)+TX, DDT(219)+TX, demephion (1037)+TX, demephion-O (1037)+TX, demephion-S(1037)+TX, demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O(1038)+TX, demeton-O-methyl (224)+TX, demeton-S (1038)+TX,demeton-S-methyl (224)+TX, demeton-S-methylsulfon (1039)+TX,diafenthiuron (226)+TX, dialifos (1042)+TX, diazinon (227)+TX,dichlofluanid (230)+TX, dichlorvos (236)+TX, dicliphos (alternativename)+TX, dicofol (242)+TX, dicrotophos (243)+TX, dienochlor (1071)+TX,dimefox (1081)+TX, dimethoate (262)+TX, dinactin (alternative name)(653)+TX, dinex (1089)+TX, dinex-diclexine (1089)+TX, dinobuton(269)+TX, dinocap (270)+TX, dinocap-4 [CCN]+TX, dinocap-6 [CCN]+TX,dinocton (1090)+TX, dinopenton (1092)+TX, dinosulfon (1097)+TX,dinoterbon (1098)+TX, dioxathion (1102)+TX, diphenyl sulfone (IUPACname) (1103)+TX, disulfiram (alternative name) [CCN]+TX, disulfoton(278)+TX, DNOC (282)+TX, dofenapyn (1113)+TX, doramectin (alternativename) [CCN]+TX, endosulfan (294)+TX, endothion (1121)+TX, EPN (297)+TX,eprinomectin (alternative name) [CCN]+TX, ethion (309)+TX,ethoate-methyl (1134)+TX, etoxazole (320)+TX, etrimfos (1142)+TX,fenazaflor (1147)+TX, fenazaquin (328)+TX, fenbutatin oxide (330)+TX,fenothiocarb (337)+TX, fenpropathrin (342)+TX, fenpyrad (alternativename)+TX, fenpyroximate (345)+TX, fenson (1157)+TX, fentrifanil(1161)+TX, fenvalerate (349)+TX, fipronil (354)+TX, fluacrypyrim(360)+TX, fluazuron (1166)+TX, flubenzimine (1167)+TX, flucycloxuron(366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX, flufenoxuron(370)+TX, flumethrin (372)+TX, fluorbenside (1174)+TX, fluvalinate(1184)+TX, FMC 1137 (development code) (1185)+TX, formetanate (405)+TX,formetanate hydrochloride (405)+TX, formothion (1192)+TX, formparanate(1193)+TX, gamma-HCH (430)+TX, glyodin (1205)+TX, halfenprox (424)+TX,heptenophos (432)+TX, hexadecyl cyclopropanecarboxylate (IUPAC/ChemicalAbstracts name) (1216)+TX, hexythiazox (441)+TX, iodomethane (IUPACname) (542)+TX, isocarbophos (alternative name) (473)+TX, isopropylO-(methoxyaminothiophosphoryl)salicylate (IUPAC name) (473)+TX,ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX, jasmolin II(696)+TX, jodfenphos (1248)+TX, lindane (430)+TX, lufenuron (490)+TX,malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan(1261)+TX, mesulfen (alternative name) [CCN]+TX, methacrifos (1266)+TX,methamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX,methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX,mevinphos (556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX,milbemycin oxime (alternative name) [CCN]+TX, mipafox (1293)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naled (567)+TX, NC-184 (compound code)+TX, NC-512(compound code)+TX, nifluridide (1309)+TX, nikkomycins (alternativename) [CCN]+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1 zinc chloridecomplex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250 (compoundcode)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydeprofos (1324)+TX,oxydisulfoton (1325)+TX, pp′-DDT (219)+TX, parathion (615)+TX,permethrin (626)+TX, petroleum oils (alternative name) (628)+TX,phenkapton (1330)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosphamidon (639)+TX,phoxim (642)+TX, pirimiphos-methyl (652)+TX, polychloroterpenes(traditional name) (1347)+TX, polynactins (alternative name) (653)+TX,proclonol (1350)+TX, profenofos (662)+TX, promacyl (1354)+TX, propargite(671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion(1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II(696)+TX, pyrethrins (696)+TX, pyridaben (699)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, quinalphos(711)+TX, quintiofos (1381)+TX, R-1492 (development code) (1382)+TX,RA-17 (development code) (1383)+TX, rotenone (722)+TX, schradan(1389)+TX, sebufos (alternative name)+TX, selamectin (alternative name)[CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, spirodiclofen(738)+TX, spiromesifen (739)+TX, SSI-121 (development code) (1404)+TX,sulfiram (alternative name) [CCN]+TX, sulfluramid (750)+TX, sulfotep(753)+TX, sulfur (754)+TX, SZI-121 (development code) (757)+TX,tau-fluvalinate (398)+TX, tebufenpyrad (763)+TX, TEPP (1417)+TX, terbam(alternative name)+TX, tetrachlorvinphos (777)+TX, tetradifon (786)+TX,tetranactin (alternative name) (653)+TX, tetrasul (1425)+TX, thiafenox(alternative name)+TX, thiocarboxime (1431)+TX, thiofanox (800)+TX,thiometon (801)+TX, thioquinox (1436)+TX, thuringiensin (alternativename) [CCN]+TX, triamiphos (1441)+TX, triarathene (1443)+TX, triazophos(820)+TX, triazuron (alternative name)+TX, trichlorfon (824)+TX,trifenofos (1455)+TX, trinactin (alternative name) (653)+TX, vamidothion(847)+TX, vaniliprole [CCN] and YI-5302 (compound code)+TX,

an algicide selected from the group of substances consisting ofbethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, coppersulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen(232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX,nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine(730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltinhydroxide (IUPAC name) (347)+TX,

an anthelmintic selected from the group of substances consisting ofabamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name)[CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin(alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX,milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternativename) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name)[CCN]+TX, spinosad (737) and thiophanate (1435)+TX,

an avicide selected from the group of substances consisting ofchloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX,pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX, a bactericideselected from the group of substances consisting of1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copperdioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name)(169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione(1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde(404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin(483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickelbis(dimethyldithiocarbamate) (IUPAC name) (1308)+TX, nitrapyrin(580)+TX, octhilinone (590)+TX, oxolinic acid (606)+TX, oxytetracycline(611)+TX, potassium hydroxyquinoline sulfate (446)+TX, probenazole(658)+TX, streptomycin (744)+TX, streptomycin sesquisulfate (744)+TX,tecloftalam (766)+TX, and thiomersal (alternative name) [CCN]+TX,

a biological agent selected from the group of substances consisting ofAdoxophyes orana GV (alternative name) (12)+TX, Agrobacteriumradiobacter (alternative name) (13)+TX, Amblyseius spp. (alternativename) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX,Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis(alternative name) (33)+TX, Aphidius colemani (alternative name)(34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographacalifornica NPV (alternative name) (38)+TX, Bacillus firmus (alternativename) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX,Bacillus thuringiensis Berliner (scientific name) (51)+TX, Bacillusthuringiensis subsp. aizawai (scientific name) (51)+TX, Bacillusthuringiensis subsp. israelensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. japonensis (scientific name) (51)+TX, Bacillusthuringiensis subsp. kurstaki (scientific name) (51)+TX, Bacillusthuringiensis subsp. tenebrionis (scientific name) (51)+TX, Beauveriabassiana (alternative name) (53)+TX, Beauveria brongniartii (alternativename) (54)+TX, Chrysoperla carnea (alternative name) (151)+TX,Cryptolaemus montrouzieri (alternative name) (178)+TX, Cydia pomonellaGV (alternative name) (191)+TX, Dacnusa sibirica (alternative name)(212)+TX, Diglyphus isaea (alternative name) (254)+TX, Encarsia formosa(scientific name) (293)+TX, Eretmocerus eremicus (alternative name)(300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX,Heterorhabditis bacteriophora and H. megidis (alternative name)(433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastixdactylopii (alternative name) (488)+TX, Macrolophus caliginosus(alternative name) (491)+TX, Mamestra brassicae NPV (alternative name)(494)+TX, Metaphycus helvolus (alternative name) (522)+TX, Metarhiziumanisopliae var. acridum (scientific name) (523)+TX, Metarhiziumanisopliae var. anisopliae (scientific name) (523)+TX, Neodiprionsertifer NPV and N. lecontei NPV (alternative name) (575)+TX, Orius spp.(alternative name) (596)+TX, Paecilomyces fumosoroseus (alternativename) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX,Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientificname) (741)+TX, Steinernema bibionis (alternative name) (742)+TX,Steinernema carpocapsae (alternative name) (742)+TX, Steinernema feltiae(alternative name) (742)+TX, Steinernema glaseri (alternative name)(742)+TX, Steinernema riobrave (alternative name) (742)+TX, Steinernemariobravis (alternative name) (742)+TX, Steinernema scapterisci(alternative name) (742)+TX, Steinernema spp. (alternative name)(742)+TX, Trichogramma spp. (alternative name) (826)+TX, Typhlodromusoccidentalis (alternative name) (844) and Verticillium lecanii(alternative name) (848)+TX,

a soil sterilant selected from the group of substances consisting ofiodomethane (IUPAC name) (542) and methyl bromide (537)+TX,

a chemosterilant selected from the group of substances consisting ofapholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan(alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif(alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa[CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid[CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX,thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name)[CCN]+TX, tretamine (alternative name) [CCN] and uredepa (alternativename) [CCN]+TX,

an insect pheromone selected from the group of substances consisting of(E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX,(E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX,(E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX,(E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX,(Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal(IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name)(437)+TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438)+TX,(Z)-icos-13-en-10-one (IUPAC name) (448)+TX, (Z)-tetradec-7-en-1-al(IUPAC name) (782)+TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783)+TX,(Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784)+TX,(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX,(9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780)+TX,(9Z,12E)-tetradeca-9,12-dien-1-yl acetate (IUPAC name) (781)+TX,14-methyloctadec-1-ene (IUPAC name) (545)+TX, 4-methylnonan-5-ol with4-methylnonan-5-one (IUPAC name) (544)+TX, alpha-multistriatin(alternative name) [CCN]+TX, brevicomin (alternative name) [CCN]+TX,codlelure (alternative name) [CCN]+TX, codlemone (alternative name)(167)+TX, cuelure (alternative name) (179)+TX, disparlure (277)+TX,dodec-8-en-1-yl acetate (IUPAC name) (286)+TX, dodec-9-en-1-yl acetate(IUPAC name) (287)+TX, dodeca-8+TX, 10-dien-1-yl acetate (IUPAC name)(284)+TX, dominicalure (alternative name) [CCN]+TX, ethyl4-methyloctanoate (IUPAC name) (317)+TX, eugenol (alternative name)[CCN]+TX, frontalin (alternative name) [CCN]+TX, gossyplure (alternativename) (420)+TX, grandlure (421)+TX, grandlure I (alternative name)(421)+TX, grandlure II (alternative name) (421)+TX, grandlure III(alternative name) (421)+TX, grandlure IV (alternative name) (421)+TX,hexalure [CCN]+TX, ipsdienol (alternative name) [CCN]+TX, ipsenol(alternative name) [CCN]+TX, japonilure (alternative name) (481)+TX,lineatin (alternative name) [CCN]+TX, litlure (alternative name)[CCN]+TX, looplure (alternative name) [CCN]+TX, medlure [CCN]+TX,megatomoic acid (alternative name) [CCN]+TX, methyl eugenol (alternativename) (540)+TX, muscalure (563)+TX, octadeca-2,13-dien-1-yl acetate(IUPAC name) (588)+TX, octadeca-3,13-dien-1-yl acetate (IUPAC name)(589)+TX, orfralure (alternative name) [CCN]+TX, oryctalure (alternativename) (317)+TX, ostramone (alternative name) [CCN]+TX, siglure [CCN]+TX,sordidin (alternative name) (736)+TX, sulcatol (alternative name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, trimedlure(839)+TX, trimedlure A (alternative name) (839)+TX, trimedlure B₁(alternative name) (839)+TX, trimedlure B₂ (alternative name) (839)+TX,trimedlure C (alternative name) (839) and trunc-call (alternative name)[CCN]+TX,

an insect repellent selected from the group of substances consisting of2-(octylthio)ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX,butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name)(1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name)(1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX,dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide[CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX,oxamate [CCN] and picaridin [CCN]+TX,

an insecticide selected from the group of substances consisting of1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX,1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX,1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX,1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX,1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX,2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name)(1451)+TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate(IUPAC name) (1066)+TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate(IUPAC/Chemical Abstracts name) (1109)+TX, 2-(2-butoxyethoxy)ethylthiocyanate (IUPAC/Chemical Abstracts name) (935)+TX,2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC/ChemicalAbstracts name) (1084)+TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name)(986)+TX, 2-chlorovinyl diethyl phosphate (IUPAC name) (984)+TX,2-imidazolidone (IUPAC name) (1225)+TX, 2-isovalerylindan-1,3-dione(IUPAC name) (1246)+TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate(IUPAC name) (1284)+TX, 2-thiocyanatoethyl laurate (IUPAC name)(1433)+TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917)+TX,3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283)+TX,4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate (IUPAC name)(1285)+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPACname) (1085)+TX, abamectin (1)+TX, acephate (2)+TX, acetamiprid (4)+TX,acethion (alternative name) [CCN]+TX, acetoprole [CCN]+TX, acrinathrin(9)+TX, acrylonitrile (IUPAC name) (861)+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, aldrin (864)+TX, allethrin (17)+TX,allosamidin (alternative name) [CCN]+TX, allyxycarb (866)+TX,alpha-cypermethrin (202)+TX, alpha-ecdysone (alternative name) [CCN]+TX,aluminium phosphide (640)+TX, amidithion (870)+TX, amidothioate(872)+TX, aminocarb (873)+TX, amiton (875)+TX, amiton hydrogen oxalate(875)+TX, amitraz (24)+TX, anabasine (877)+TX, athidathion (883)+TX, AVI382 (compound code)+TX, AZ 60541 (compound code)+TX, azadirachtin(alternative name) (41)+TX, azamethiphos (42)+TX, azinphos-ethyl(44)+TX, azinphos-methyl (45)+TX, azothoate (889)+TX, Bacillusthuringiensis delta endotoxins (alternative name) (52)+TX, bariumhexafluorosilicate (alternative name) [CCN]+TX, barium polysulfide(IUPAC/Chemical Abstracts name) (892)+TX, barthrin [CCN]+TX, Bayer22/190 (development code) (893)+TX, Bayer 22408 (development code)(894)+TX, bendiocarb (58)+TX, benfuracarb (60)+TX, bensultap (66)+TX,beta-cyfluthrin (194)+TX, beta-cypermethrin (203)+TX, bifenthrin(76)+TX, bioallethrin (78)+TX, bioallethrin S-cyclopentenyl isomer(alternative name) (79)+TX, bioethanomethrin [CCN]+TX, biopermethrin(908)+TX, bioresmethrin (80)+TX, bis(2-chloroethyl) ether (IUPAC name)(909)+TX, bistrifluron (83)+TX, borax (86)+TX, brofenvalerate(alternative name)+TX, bromfenvinfos (914)+TX, bromocyclen (918)+TX,bromo-DDT (alternative name) [CCN]+TX, bromophos (920)+TX,bromophos-ethyl (921)+TX, bufencarb (924)+TX, buprofezin (99)+TX,butacarb (926)+TX, butathiofos (927)+TX, butocarboxim (103)+TX, butonate(932)+TX, butoxycarboxim (104)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, calcium arsenate [CCN]+TX, calcium cyanide (444)+TX,calcium polysulfide (IUPAC name) (111)+TX, camphechlor (941)+TX,carbanolate (943)+TX, carbaryl (115)+TX, carbofuran (118)+TX, carbondisulfide (IUPAC/Chemical Abstracts name) (945)+TX, carbon tetrachloride(IUPAC name) (946)+TX, carbophenothion (947)+TX, carbosulfan (119)+TX,cartap (123)+TX, cartap hydrochloride (123)+TX, cevadine (alternativename) (725)+TX, chlorbicyclen (960)+TX, chlordane (128)+TX, chlordecone(963)+TX, chlordimeform (964)+TX, chlordimeform hydrochloride (964)+TX,chlorethoxyfos (129)+TX, chlorfenapyr (130)+TX, chlorfenvinphos(131)+TX, chlorfluazuron (132)+TX, chlormephos (136)+TX, chloroform[CCN]+TX, chloropicrin (141)+TX, chlorphoxim (989)+TX, chlorprazophos(990)+TX, chlorpyrifos (145)+TX, chlorpyrifos-methyl (146)+TX,chlorthiophos (994)+TX, chromafenozide (150)+TX, cinerin I (696)+TX,cinerin II (696)+TX, cinerins (696)+TX, cis-resmethrin (alternativename)+TX, cismethrin (80)+TX, clocythrin (alternative name)+TX,cloethocarb (999)+TX, closantel (alternative name) [CCN]+TX,clothianidin (165)+TX, copper acetoarsenite [CCN]+TX, copper arsenate[CCN]+TX, copper oleate [CCN]+TX, coumaphos (174)+TX, coumithoate(1006)+TX, crotamiton (alternative name) [CCN]+TX, crotoxyphos(1010)+TX, crufomate (1011)+TX, cryolite (alternative name) (177)+TX, CS708 (development code) (1012)+TX, cyanofenphos (1019)+TX, cyanophos(184)+TX, cyanthoate (1020)+TX, cyclethrin [CCN]+TX, cycloprothrin(188)+TX, cyfluthrin (193)+TX, cyhalothrin (196)+TX, cypermethrin(201)+TX, cyphenothrin (206)+TX, cyromazine (209)+TX, cythioate(alternative name) [CCN]+TX, d-limonene (alternative name) [CCN]+TX,d-tetramethrin (alternative name) (788)+TX, DAEP (1031)+TX, dazomet(216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, deltamethrin (223)+TX,demephion (1037)+TX, demephion-O (1037)+TX, demephion-S (1037)+TX,demeton (1038)+TX, demeton-methyl (224)+TX, demeton-O (1038)+TX,demeton-O-methyl (224)+TX, demeton-S (1038)+TX, demeton-S-methyl(224)+TX, demeton-S-methylsulphon (1039)+TX, diafenthiuron (226)+TX,dialifos (1042)+TX, diamidafos (1044)+TX, diazinon (227)+TX, dicapthon(1050)+TX, dichlofenthion (1051)+TX, dichlorvos (236)+TX, dicliphos(alternative name)+TX, dicresyl (alternative name) [CCN]+TX, dicrotophos(243)+TX, dicyclanil (244)+TX, dieldrin (1070)+TX, diethyl5-methylpyrazol-3-yl phosphate (IUPAC name) (1076)+TX, diflubenzuron(250)+TX, dilor (alternative name) [CCN]+TX, dimefluthrin [CCN]+TX,dimefox (1081)+TX, dimetan (1085)+TX, dimethoate (262)+TX, dimethrin(1083)+TX, dimethylvinphos (265)+TX, dimetilan (1086)+TX, dinex(1089)+TX, dinex-diclexine (1089)+TX, dinoprop (1093)+TX, dinosam(1094)+TX, dinoseb (1095)+TX, dinotefuran (271)+TX, diofenolan(1099)+TX, dioxabenzofos (1100)+TX, dioxacarb (1101)+TX, dioxathion(1102)+TX, disulfoton (278)+TX, dithicrofos (1108)+TX, DNOC (282)+TX,doramectin (alternative name) [CCN]+TX, DSP (1115)+TX, ecdysterone(alternative name) [CCN]+TX, EI 1642 (development code) (1118)+TX,emamectin (291)+TX, emamectin benzoate (291)+TX, EMPC (1120)+TX,empenthrin (292)+TX, endosulfan (294)+TX, endothion (1121)+TX, endrin(1122)+TX, EPBP (1123)+TX, EPN (297)+TX, epofenonane (1124)+TX,eprinomectin (alternative name) [CCN]+TX, esfenvalerate (302)+TX,etaphos (alternative name) [CCN]+TX, ethiofencarb (308)+TX, ethion(309)+TX, ethiprole (310)+TX, ethoate-methyl (1134)+TX, ethoprophos(312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alternativename) (1056)+TX, ethylene dibromide (316)+TX, ethylene dichloride(chemical name) (1136)+TX, ethylene oxide [CCN]+TX, etofenprox (319)+TX,etrimfos (1142)+TX, EXD (1143)+TX, famphur (323)+TX, fenamiphos(326)+TX, fenazaflor (1147)+TX, fenchlorphos (1148)+TX, fenethacarb(1149)+TX, fenfluthrin (1150)+TX, fenitrothion (335)+TX, fenobucarb(336)+TX, fenoxacrim (1153)+TX, fenoxycarb (340)+TX, fenpirithrin(1155)+TX, fenpropathrin (342)+TX, fenpyrad (alternative name)+TX,fensulfothion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX,fenvalerate (349)+TX, fipronil (354)+TX, flonicamid (358)+TX,flubendiamide (CAS. Reg. No.: 272451-65-7)+TX, flucofuron (1168)+TX,flucycloxuron (366)+TX, flucythrinate (367)+TX, fluenetil (1169)+TX,flufenerim [CCN]+TX, flufenoxuron (370)+TX, flufenprox (1171)+TX,flumethrin (372)+TX, fluvalinate (1184)+TX, FMC 1137 (development code)(1185)+TX, fonofos (1191)+TX, formetanate (405)+TX, formetanatehydrochloride (405)+TX, formothion (1192)+TX, formparanate (1193)+TX,fosmethilan (1194)+TX, fospirate (1195)+TX, fosthiazate (408)+TX,fosthietan (1196)+TX, furathiocarb (412)+TX, furethrin (1200)+TX,gamma-cyhalothrin (197)+TX, gamma-HCH (430)+TX, guazatine (422)+TX,guazatine acetates (422)+TX, GY-81 (development code) (423)+TX,halfenprox (424)+TX, halofenozide (425)+TX, HCH (430)+TX, HEOD(1070)+TX, heptachlor (1211)+TX, heptenophos (432)+TX, heterophos[CCN]+TX, hexaflumuron (439)+TX, HHDN (864)+TX, hydramethylnon (443)+TX,hydrogen cyanide (444)+TX, hydroprene (445)+TX, hyquincarb (1223)+TX,imidacloprid (458)+TX, imiprothrin (460)+TX, indoxacarb (465)+TX,iodomethane (IUPAC name) (542)+TX, IPSP (1229)+TX, isazofos (1231)+TX,isobenzan (1232)+TX, isocarbophos (alternative name) (473)+TX, isodrin(1235)+TX, isofenphos (1236)+TX, isolane (1237)+TX, isoprocarb (472)+TX,isopropyl O-(methoxy-aminothiophosphoryl)salicylate (IUPAC name)(473)+TX, isoprothiolane (474)+TX, isothioate (1244)+TX, isoxathion(480)+TX, ivermectin (alternative name) [CCN]+TX, jasmolin I (696)+TX,jasmolin II (696)+TX, jodfenphos (1248)+TX, juvenile hormone I(alternative name) [CCN]+TX, juvenile hormone II (alternative name)[CCN]+TX, juvenile hormone III (alternative name) [CCN]+TX, kelevan(1249)+TX, kinoprene (484)+TX, lambda-cyhalothrin (198)+TX, leadarsenate [CCN]+TX, lepimectin (CCN)+TX, leptophos (1250)+TX, lindane(430)+TX, lirimfos (1251)+TX, lufenuron (490)+TX, lythidathion(1253)+TX, m-cumenyl methylcarbamate (IUPAC name) (1014)+TX, magnesiumphosphide (IUPAC name) (640)+TX, malathion (492)+TX, malonoben(1254)+TX, mazidox (1255)+TX, mecarbam (502)+TX, mecarphon (1258)+TX,menazon (1260)+TX, mephosfolan (1261)+TX, mercurous chloride (513)+TX,mesulfenfos (1263)+TX, metaflumizone (CCN)+TX, metam (519)+TX,metam-potassium (alternative name) (519)+TX, metam-sodium (519)+TX,methacrifos (1266)+TX, methamidophos (527)+TX, methanesulfonyl fluoride(IUPAC/Chemical Abstracts name) (1268)+TX, methidathion (529)+TX,methiocarb (530)+TX, methocrotophos (1273)+TX, methomyl (531)+TX,methoprene (532)+TX, methoquin-butyl (1276)+TX, methothrin (alternativename) (533)+TX, methoxychlor (534)+TX, methoxyfenozide (535)+TX, methylbromide (537)+TX, methyl isothiocyanate (543)+TX, methylchloroform(alternative name) [CCN]+TX, methylene chloride [CCN]+TX, metofluthrin[CCN]+TX, metolcarb (550)+TX, metoxadiazone (1288)+TX, mevinphos(556)+TX, mexacarbate (1290)+TX, milbemectin (557)+TX, milbemycin oxime(alternative name) [CCN]+TX, mipafox (1293)+TX, mirex (1294)+TX,monocrotophos (561)+TX, morphothion (1300)+TX, moxidectin (alternativename) [CCN]+TX, naftalofos (alternative name) [CCN]+TX, naled (567)+TX,naphthalene (IUPAC/Chemical Abstracts name) (1303)+TX, NC-170(development code) (1306)+TX, NC-184 (compound code)+TX, nicotine(578)+TX, nicotine sulfate (578)+TX, nifluridide (1309)+TX, nitenpyram(579)+TX, nithiazine (1311)+TX, nitrilacarb (1313)+TX, nitrilacarb 1:1zinc chloride complex (1313)+TX, NNI-0101 (compound code)+TX, NNI-0250(compound code)+TX, nornicotine (traditional name) (1319)+TX, novaluron(585)+TX, noviflumuron (586)+TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate (IUPAC name) (1057)+TX, O,O-diethylO-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate (IUPAC name)(1074)+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate (IUPAC name) (1075)+TX, O,O,O′,O′-tetrapropyldithiopyrophosphate (IUPAC name) (1424)+TX, oleic acid (IUPAC name)(593)+TX, omethoate (594)+TX, oxamyl (602)+TX, oxydemeton-methyl(609)+TX, oxydeprofos (1324)+TX, oxydisulfoton (1325)+TX, pp′-DDT(219)+TX, para-dichlorobenzene [CCN]+TX, parathion (615)+TX,parathion-methyl (616)+TX, penfluron (alternative name) [CCN]+TX,pentachlorophenol (623)+TX, pentachlorophenyl laurate (IUPAC name)(623)+TX, permethrin (626)+TX, petroleum oils (alternative name)(628)+TX, PH 60-38 (development code) (1328)+TX, phenkapton (1330)+TX,phenothrin (630)+TX, phenthoate (631)+TX, phorate (636)+TX, phosalone(637)+TX, phosfolan (1338)+TX, phosmet (638)+TX, phosnichlor (1339)+TX,phosphamidon (639)+TX, phosphine (IUPAC name) (640)+TX, phoxim (642)+TX,phoxim-methyl (1340)+TX, pirimetaphos (1344)+TX, pirimicarb (651)+TX,pirimiphos-ethyl (1345)+TX, pirimiphos-methyl (652)+TX,polychlorodicyclopentadiene isomers (IUPAC name) (1346)+TX,polychloroterpenes (traditional name) (1347)+TX, potassium arsenite[CCN]+TX, potassium thiocyanate [CCN]+TX, prallethrin (655)+TX,precocene I (alternative name) [CCN]+TX, precocene II (alternative name)[CCN]+TX, precocene Ill (alternative name) [CCN]+TX, primidophos(1349)+TX, profenofos (662)+TX, profluthrin [CCN]+TX, promacyl(1354)+TX, promecarb (1355)+TX, propaphos (1356)+TX, propetamphos(673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothiofos(686)+TX, prothoate (1362)+TX, protrifenbute [CCN]+TX, pymetrozine(688)+TX, pyraclofos (689)+TX, pyrazophos (693)+TX, pyresmethrin(1367)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins(696)+TX, pyridaben (699)+TX, pyridalyl (700)+TX, pyridaphenthion(701)+TX, pyrimidifen (706)+TX, pyrimitate (1370)+TX, pyriproxyfen(708)+TX, quassia (alternative name) [CCN]+TX, quinalphos (711)+TX,quinalphos-methyl (1376)+TX, quinothion (1380)+TX, quintiofos (1381)+TX,R-1492 (development code) (1382)+TX, rafoxanide (alternative name)[CCN]+TX, resmethrin (719)+TX, rotenone (722)+TX, RU 15525 (developmentcode) (723)+TX, RU 25475 (development code) (1386)+TX, ryania(alternative name) (1387)+TX, ryanodine (traditional name) (1387)+TX,sabadilla (alternative name) (725)+TX, schradan (1389)+TX, sebufos(alternative name)+TX, selamectin (alternative name) [CCN]+TX, SI-0009(compound code)+TX, SI-0205 (compound code)+TX, SI-0404 (compoundcode)+TX, SI-0405 (compound code)+TX, silafluofen (728)+TX, SN 72129(development code) (1397)+TX, sodium arsenite [CCN]+TX, sodium cyanide(444)+TX, sodium fluoride (IUPAC/Chemical Abstracts name) (1399)+TX,sodium hexafluorosilicate (1400)+TX, sodium pentachlorophenoxide(623)+TX, sodium selenate (IUPAC name) (1401)+TX, sodium thiocyanate[CCN]+TX, sophamide (1402)+TX, spinosad (737)+TX, spiromesifen (739)+TX,spirotetrmat (CCN)+TX, sulcofuron (746)+TX, sulcofuron-sodium (746)+TX,sulfluramid (750)+TX, sulfotep (753)+TX, sulfuryl fluoride (756)+TX,sulprofos (1408)+TX, tar oils (alternative name) (758)+TX,tau-fluvalinate (398)+TX, tazimcarb (1412)+TX, TDE (1414)+TX,tebufenozide (762)+TX, tebufenpyrad (763)+TX, tebupirimfos (764)+TX,teflubenzuron (768)+TX, tefluthrin (769)+TX, temephos (770)+TX, TEPP(1417)+TX, terallethrin (1418)+TX, terbam (alternative name)+TX,terbufos (773)+TX, tetrachloroethane [CCN]+TX, tetrachlorvinphos(777)+TX, tetramethrin (787)+TX, theta-cypermethrin (204)+TX,thiacloprid (791)+TX, thiafenox (alternative name)+TX, thiamethoxam(792)+TX, thicrofos (1428)+TX, thiocarboxime (1431)+TX, thiocyclam(798)+TX, thiocyclam hydrogen oxalate (798)+TX, thiodicarb (799)+TX,thiofanox (800)+TX, thiometon (801)+TX, thionazin (1434)+TX, thiosultap(803)+TX, thiosultap-sodium (803)+TX, thuringiensin (alternative name)[CCN]+TX, tolfenpyrad (809)+TX, tralomethrin (812)+TX, transfluthrin(813)+TX, transpermethrin (1440)+TX, triamiphos (1441)+TX, triazamate(818)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,trichlorfon (824)+TX, trichlormetaphos-3 (alternative name) [CCN]+TX,trichloronat (1452)+TX, trifenofos (1455)+TX, triflumuron (835)+TX,trimethacarb (840)+TX, triprene (1459)+TX, vamidothion (847)+TX,vaniliprole [CCN]+TX, veratridine (alternative name) (725)+TX, veratrine(alternative name) (725)+TX, XMC (853)+TX, xylylcarb (854)+TX, YI-5302(compound code)+TX, zeta-cypermethrin (205)+TX, zetamethrin (alternativename)+TX, zinc phosphide (640)+TX, zolaprofos (1469) and ZXI 8901(development code) (858)+TX, cyantraniliprole [736994-63-19+TX,chlorantraniliprole [500008-45-7]+TX, cyenopyrafen [560121-52-0]+TX,cyflumetofen [400882-07-7]+TX, pyrifluquinazon [337458-27-2]+TX,spinetoram [187166-40-1+187166-15-0]+TX, spirotetramat [203313-25-1]+TX,sulfoxaflor [946578-00-3]+TX, flufiprole [704886-18-0]+TX, meperfluthrin[915288-13-0]+TX, tetramethylfluthrin [84937-88-2]+TX, triflumezopyrim(disclosed in WO 2012/092115)+TX, fluxametamide (WO 2007/026965)+TX,epsilon-metofluthrin [240494-71-7]+TX, epsilon-momfluorothrin[1065124-65-3]+TX, fluazaindolizine [1254304-22-7]+TX, chloroprallethrin[399572-87-3]+TX, fluxametamide [928783-29-3]+TX, cyhalodiamide[1262605-53-7]+TX, tioxazafen [330459-31-9]+TX, broflanilide[1207727-04-5]+TX, flufiprole [704886-18-0]+TX, cyclaniliprole[1031756-98-5]+TX, tetraniliprole [1229654-66-3]+TX, guadipyr (describedin WO2010/060231)+TX, cycloxaprid (described in WO2005/077934)+TX,

a molluscicide selected from the group of substances consisting ofbis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX,calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite[CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate(IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX,niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol(623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX,thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX,trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) andtriphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole[394730-71-3]+TX,

a nematicide selected from the group of substances consisting ofAKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/ChemicalAbstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstractsname) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPACname) (1063)+TX, 1,3-dichloropropene (233)+TX,3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstractsname) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name)(980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPACname) (1286)+TX, 6-isopentenylaminopurine (alternative name) (210)+TX,abamectin (1)+TX, acetoprole [CCN]+TX, alanycarb (15)+TX, aldicarb(16)+TX, aldoxycarb (863)+TX, AZ 60541 (compound code)+TX, benclothiaz[CCN]+TX, benomyl (62)+TX, butylpyridaben (alternative name)+TX,cadusafos (109)+TX, carbofuran (118)+TX, carbon disulfide (945)+TX,carbosulfan (119)+TX, chloropicrin (141)+TX, chlorpyrifos (145)+TX,cloethocarb (999)+TX, cytokinins (alternative name) (210)+TX, dazomet(216)+TX, DBCP (1045)+TX, DCIP (218)+TX, diamidafos (1044)+TX,dichlofenthion (1051)+TX, dicliphos (alternative name)+TX, dimethoate(262)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX,emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX,ethoprophos (312)+TX, ethylene dibromide (316)+TX, fenamiphos (326)+TX,fenpyrad (alternative name)+TX, fensulfothion (1158)+TX, fosthiazate(408)+TX, fosthietan (1196)+TX, furfural (alternative name) [CCN]+TX,GY-81 (development code) (423)+TX, heterophos [CCN]+TX, iodomethane(IUPAC name) (542)+TX, isamidofos (1230)+TX, isazofos (1231)+TX,ivermectin (alternative name) [CCN]+TX, kinetin (alternative name)(210)+TX, mecarphon (1258)+TX, metam (519)+TX, metam-potassium(alternative name) (519)+TX, metam-sodium (519)+TX, methyl bromide(537)+TX, methyl isothiocyanate (543)+TX, milbemycin oxime (alternativename) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, Myrotheciumverrucaria composition (alternative name) (565)+TX, NC-184 (compoundcode)+TX, oxamyl (602)+TX, phorate (636)+TX, phosphamidon (639)+TX,phosphocarb [CCN]+TX, sebufos (alternative name)+TX, selamectin(alternative name) [CCN]+TX, spinosad (737)+TX, terbam (alternativename)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC/ChemicalAbstracts name) (1422)+TX, thiafenox (alternative name)+TX, thionazin(1434)+TX, triazophos (820)+TX, triazuron (alternative name)+TX,xylenols [CCN]+TX, YI-5302 (compound code) and zeatin (alternative name)(210)+TX, fluensulfone [318290-98-1]+TX,

a nitrification inhibitor selected from the group of substancesconsisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,

a plant activator selected from the group of substances consisting ofacibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) andReynoutria sachalinensis extract (alternative name) (720)+TX,

a rodenticide selected from the group of substances consisting of2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX,4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX,alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu(880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX,bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX,bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX,chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX,coumachlor (1004)+TX, coumafuryl (1005)+TX, coumatetralyl (175)+TX,crimidine (1009)+TX, difenacoum (246)+TX, difethialone (249)+TX,diphacinone (273)+TX, ergocalciferol (301)+TX, flocoumafen (357)+TX,fluoroacetamide (379)+TX, flupropadine (1183)+TX, flupropadinehydrochloride (1183)+TX, gamma-HCH (430)+TX, HCH (430)+TX, hydrogencyanide (444)+TX, iodomethane (IUPAC name) (542)+TX, lindane (430)+TX,magnesium phosphide (IUPAC name) (640)+TX, methyl bromide (537)+TX,norbormide (1318)+TX, phosacetim (1336)+TX, phosphine (IUPAC name)(640)+TX, phosphorus [CCN]+TX, pindone (1341)+TX, potassium arsenite[CCN]+TX, pyrinuron (1371)+TX, scilliroside (1390)+TX, sodium arsenite[CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX,strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zincphosphide (640)+TX,

a synergist selected from the group of substances consisting of2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934)+TX,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX,farnesol with nerolidol (alternative name) (324)+TX, MB-599 (developmentcode) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide(649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (developmentcode) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide(1406)+TX,

an animal repellent selected from the group of substances consisting ofanthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX,copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene(chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates(422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX,thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram(856)+TX, a virucide selected from the group of substances consisting ofimanin (alternative name) [CCN] and ribavirin (alternative name)[CCN]+TX,

a wound protectant selected from the group of substances consisting ofmercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl(802)+TX,

and biologically active compounds selected from the group consisting ofazaconazole (60207-31-0]+TX, bitertanol [70585-36-3]+TX, bromuconazole[116255-48-2]+TX, cyproconazole [94361-06-5]+TX, difenoconazole[119446-68-3]+TX, diniconazole [83657-24-3]+TX, epoxiconazole[106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fluquinconazole[136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol[76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX,imibenconazole [86598-92-7]+TX, ipconazole [125225-28-7]+TX, metconazole[125116-23-6]+TX, myclobutanil [88671-89-0]+TX, pefurazoate[101903-30-4]+TX, penconazole [66246-88-6]+TX, prothioconazole[178928-70-6]+TX, pyrifenox [88283-41-4]+TX, prochloraz [67747-09-5]+TX,propiconazole [60207-90-1]+TX, simeconazole [149508-90-7]+TX,tebuconazole [107534-96-3]+TX, tetraconazole [112281-77-3]+TX,triadimefon [43121-43-3]+TX, triadimenol [55219-65-3]+TX, triflumizole[99387-89-0]+TX, triticonazole [131983-72-7]+TX, ancymidol[12771-68-5]+TX, fenarimol [60168-88-9]+TX, nuarimol [63284-71-9]+TX,bupirimate [41483-43-6]+TX, dimethirimol [5221-53-4]+TX, ethirimol[23947-60-6]+TX, dodemorph [1593-77-7]+TX, fenpropidine [67306-00-7]+TX,fenpropimorph [67564-91-4]+TX, spiroxamine [118134-30-8]+TX, tridemorph[81412-43-3]+TX, cyprodinil [121552-61-2]+TX, mepanipyrim[110235-47-7]+TX, pyrimethanil [53112-28-0]+TX, fenpiclonil[74738-17-3]+TX, fludioxonil [131341-86-1]+TX, benalaxyl[71626-11-4]+TX, furalaxyl [57646-30-7]+TX, metalaxyl [57837-19-1]+TX,R-metalaxyl [70630-17-0]+TX, ofurace [58810-48-3]+TX, oxadixyl[77732-09-3]+TX, benomyl [17804-35-2]+TX, carbendazim [10605-21-7]+TX,debacarb [62732-91-6]+TX, fuberidazole [3878-19-1]+TX, thiabendazole[148-79-8]+TX, chlozolinate [84332-86-5]+TX, dichlozoline[24201-58-9]+TX, iprodione [36734-19-7]+TX, myclozoline [54864-61-8]+TX,procymidone [32809-16-8]+TX, vinclozoline [50471-44-8]+TX, boscalid[188425-85-6]+TX, carboxin [5234-68-4]+TX, fenfuram [24691-80-3]+TX,flutolanil [66332-96-5]+TX, mepronil [55814-41-0]+TX, oxycarboxin[5259-88-1]+TX, penthiopyrad [183675-82-3]+TX, thifluzamide[130000-40-7]+TX, guazatine [108173-90-6]+TX, dodine [2439-10-3][112-65-2] (free base)+TX, iminoctadine [13516-27-3]+TX, azoxystrobin[131860-33-8]+TX, dimoxystrobin [149961-52-4]+TX, enestroburin {Proc.BCPC, Int. Congr., Glasgow, 2003, 1, 93}+TX, fluoxastrobin[361377-29-9]+TX, kresoxim-methyl [143390-89-0]+TX, metominostrobin[133408-50-1]+TX, trifloxystrobin [141517-21-7]+TX, orysastrobin[248593-16-0]+TX, picoxystrobin [117428-22-5]+TX, pyraclostrobin[175013-18-0]+TX, ferbam [14484-64-1]+TX, mancozeb [8018-01-7]+TX, maneb[12427-38-2]+TX, metiram [9006-42-2]+TX, propineb [12071-83-9]+TX,thiram [137-26-8]+TX, zineb [12122-67-7]+TX, ziram [137-30-4]+TX,captafol [2425-06-1]+TX, captan [133-06-2]+TX, dichlofluanid[1085-98-9]+TX, fluoroimide [41205-21-4]+TX, folpet [133-07-3]+TX,tolylfluanid [731-27-1]+TX, bordeaux mixture [8011-63-0]+TX,copperhydroxid [20427-59-2]+TX, copperoxychlorid [1332-40-7]+TX,coppersulfat [7758-98-7]+TX, copperoxid [1317-39-1]+TX, mancopper[53988-93-5]+TX, oxine-copper [10380-28-6]+TX, dinocap [131-72-6]+TX,nitrothal-isopropyl [10552-74-6]+TX, edifenphos [17109-49-8]+TX,iprobenphos [26087-47-8]+TX, isoprothiolane [50512-35-1]+TX, phosdiphen[36519-00-3]+TX, pyrazophos [13457-18-6]+TX, tolclofos-methyl[57018-04-9]+TX, acibenzolar-S-methyl [135158-54-2]+TX, anilazine[101-05-3]+TX, benthiavalicarb [413615-35-7]+TX, blasticidin-S[2079-00-7]+TX, chinomethionat [2439-01-2]+TX, chloroneb [2675-77-6]+TX,chlorothalonil [1897-45-6]+TX, cyflufenamid [180409-60-3]+TX, cymoxanil[57966-95-7]+TX, dichlone [117-80-6]+TX, diclocymet [139920-32-4]+TX,diclomezine [62865-36-5]+TX, dicloran [99-30-9]+TX, diethofencarb[87130-20-9]+TX, dimethomorph [110488-70-5]+TX, SYP-L190 (Flumorph)[211867-47-9]+TX, dithianon [3347-22-6]+TX, ethaboxam [162650-77-3]+TX,etridiazole [2593-15-9]+TX, famoxadone [131807-57-3]+TX, fenamidone[161326-34-7]+TX, fenoxanil [115852-48-7]+TX, fentin [668-34-8]+TX,ferimzone [89269-64-7]+TX, fluazinam [79622-59-6]+TX, fluopicolide[239110-15-7]+TX, flusulfamide [106917-52-6]+TX, fenhexamid[126833-17-8]+TX, fosetyl-aluminium [39148-24-8]+TX, hymexazol[10004-44-1]+TX, iprovalicarb [140923-17-7]+TX, IKF-916 (Cyazofamid)[120116-88-3]+TX, kasugamycin [6980-18-3]+TX, methasulfocarb[66952-49-6]+TX, metrafenone [220899-03-6]+TX, pencycuron[66063-05-6]+TX, phthalide [27355-22-2]+TX, polyoxins [11113-80-7]+TX,probenazole [27605-76-1]+TX, propamocarb [25606-41-1]+TX, proquinazid[189278-12-4]+TX, pyroquilon [57369-32-1]+TX, quinoxyfen[124495-18-7]+TX, quintozene [82-68-8]+TX, sulfur [7704-34-9]+TX,tiadinil [223580-51-6]+TX, triazoxide [72459-58-6]+TX, tricyclazole[41814-78-2]+TX, triforine [26644-46-2]+TX, validamycin [37248-47-8]+TX,zoxamide (RH7281) [156052-68-5]+TX, mandipropamid [374726-62-2]+TX,isopyrazam [881685-58-1]+TX, sedaxane [874967-67-6]+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide(disclosed in WO 2007/048556)+TX,3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid(3′,4′,5′-trifluoro-biphenyl-2-yl)-amide (disclosed in WO2006/087343)+TX,[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11Hnaphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl-cyclopropanecarboxylate[915972-17-7]+TX and1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide[926914-55-8]+TX.

The references in brackets behind the active ingredients, e.g.[3878-19-1] refer to the Chemical Abstracts Registry number. The abovedescribed mixing partners are known. Where the active ingredients areincluded in “The Pesticide Manual” [The Pesticide Manual—A WorldCompendium; Thirteenth Edition; Editor: C. D. S. TomLin; The BritishCrop Protection Council], they are described therein under the entrynumber given in round brackets hereinabove for the particular compound;for example, the compound “abamectin” is described under entry number(1). Where “[CCN]” is added hereinabove to the particular compound, thecompound in question is included in the “Compendium of Pesticide CommonNames”, which is accessible on the internet [A. Wood; Compendium ofPesticide Common Names, Copyright 1995-2004]; for example, the compound“acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred tohereinabove by a so-called “common name”, the relevant “ISO common name”or another “common name” being used in individual cases. If thedesignation is not a “common name”, the nature of the designation usedinstead is given in round brackets for the particular compound; in thatcase, the IUPAC name, the IUPAC/Chemical Abstracts name, a “chemicalname”, a “traditional name”, a “compound name” or a “develoment code” isused or, if neither one of those designations nor a “common name” isused, an “alternative name” is employed. “CAS Reg. No” means theChemical Abstracts Registry Number.

The active ingredient mixture of the compounds of formula I selectedfrom Tables 1 to 6 with active ingredients described above comprises acompound selected from Tables 1 to 6 and an active ingredient asdescribed above preferably in a mixing ratio of from 100:1 to 1:6000,especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to1:20, even more especially from 10:1 to 1:10, very especially from 5:1and 1:5, special preference being given to a ratio of from 2:1 to 1:2,and a ratio of from 4:1 to 2:1 being likewise preferred, above all in aratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750.Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controllingpests, which comprises applying a composition comprising a mixture asdescribed above to the pests or their environment, with the exception ofa method for treatment of the human or animal body by surgery or therapyand diagnostic methods practised on the human or animal body.

The mixtures comprising a compound of formula I selected from Tables 1to 6 and one or more active ingredients as described above can beapplied, for example, in a single “ready-mix” form, in a combined spraymixture composed from separate formulations of the single activeingredient components, such as a “tank-mix”, and in a combined use ofthe single active ingredients when applied in a sequential manner, i.e.one after the other with a reasonably short period, such as a few hoursor days. The order of applying the compounds of formula I selected fromTables 1 to 6 and the active ingredients as described above is notessential for working the present invention.

The compositions according to the invention can also comprise furthersolid or liquid auxiliaries, such as stabilizers, for exampleunepoxidized or epoxidized vegetable oils (for example epoxidizedcoconut oil, rapeseed oil or soya oil), antifoams, for example siliconeoil, preservatives, viscosity regulators, binders and/or tackifiers,fertilizers or other active ingredients for achieving specific effects,for example bactericides, fungicides, nematocides, plant activators,molluscicides or herbicides.

The compositions according to the invention are prepared in a mannerknown per se, in the absence of auxiliaries for example by grinding,screening and/or compressing a solid active ingredient and in thepresence of at least one auxiliary for example by intimately mixingand/or grinding the active ingredient with the auxiliary (auxiliaries).These processes for the preparation of the compositions and the use ofthe compounds I for the preparation of these compositions are also asubject of the invention.

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is generally 1 to 2000 g of active ingredient per hectare, inparticular 10 to 1000 g/ha, preferably 10 to 600 g/ha.

A preferred method of application in the field of crop protection isapplication to the foliage of the plants (foliar application), it beingpossible to select frequency and rate of application to match the dangerof infestation with the pest in question. Alternatively, the activeingredient can reach the plants via the root system (systemic action),by drenching the locus of the plants with a liquid composition or byincorporating the active ingredient in solid form into the locus of theplants, for example into the soil, for example in the form of granules(soil application). In the case of paddy rice crops, such granules canbe metered into the flooded paddy-field.

The compounds of the invention and compositions thereof are also besuitable for the protection of plant propagation material, for exampleseeds, such as fruit, tubers or kernels, or nursery plants, againstpests of the abovementioned type. The propagation material can betreated with the compound prior to planting, for example seed can betreated prior to sowing. Alternatively, the compound can be applied toseed kernels (coating), either by soaking the kernels in a liquidcomposition or by applying a layer of a solid composition. It is alsopossible to apply the compositions when the propagation material isplanted to the site of application, for example into the seed furrowduring drilling. These treatment methods for plant propagation materialand the plant propagation material thus treated are further subjects ofthe invention. Typical treatment rates would depend on the plant andpest/fungi to be controlled and are generally between 1 to 200 grams per100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds,such as between 10 to 100 grams per 100 kg of seeds.

The term seed embraces seeds and plant propagules of all kinds includingbut not limited to true seeds, seed pieces, suckers, corns, bulbs,fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like andmeans in a preferred embodiment true seeds.

The present invention also comprises seeds coated or treated with orcontaining a compound of formula I. The term “coated or treated withand/or containing” generally signifies that the active ingredient is forthe most part on the surface of the seed at the time of application,although a greater or lesser part of the ingredient may penetrate intothe seed material, depending on the method of application. When the saidseed product is (re)planted, it may absorb the active ingredient. In anembodiment, the present invention makes available a plant propagationmaterial adhered thereto with a compound of formula (I). Further, it ishereby made available, a composition comprising a plant propagationmaterial treated with a compound of formula (I).

Seed treatment comprises all suitable seed treatment techniques known inthe art, such as seed dressing, seed coating, seed dusting, seed soakingand seed pelleting. The seed treatment application of the compoundformula (I) can be carried out by any known methods, such as spraying orby dusting the seeds before sowing or during the sowing/planting of theseeds.

BIOLOGICAL EXAMPLES Example B1: Activity Against Spodoptera littoralis(Egyptian Cotton Leaf Worm) Larvicide, Feeding/Residual ContactActivity, Preventive

Cotton leaf discs were placed on agar in a 24-well microtiter plate andsprayed with test solutions.

After drying, the leaf discs were infested with 5 L1 larvae. The sampleswere checked for mortality, repellent effect, feeding behaviour, andgrowth regulation 3 days after treatment (DAT).

In this test, compounds P1, P2, P4, P5, P7, P10, P12, P15, P16, P20,P21, P22, P24, P33, P46, P48, P56, P59, P60, P61, P62, P63, P64, P65,P66, P68, P69 and P71 showed an activity of over 80% at a concentrationof 400 ppm.

Example B2: Activity Against Spodoptera littoralis (Egyptian Cotton LeafWorm) (Systemic Activity)

Test compounds were applied by pipette into 24 well plates and mixedwith agar. Lettuce seeds were placed on the agar and the multi wellplate is closed by another plate which contains also agar. After 7 daysthe roots have absorbed the compound and the lettuce has grown into thelid plate. The lettuce leaves were now cut off into the lid plate.Spodoptera eggs were pipetted through a plastic stencil on a humid gelblotting paper and the plate closed with it. The samples are checked formortality, repellent effect, feeding behavior, and growth regulation 5days after infestation.

In this test, compounds P2, P5, P7, P33, P60, P65, P66 and P68 showed anactivity of at least 80% at a concentration of 12.5 ppm.

Example B3: Activity Against Plutella xylostella (Diamond Back Moth)(Larvicide, Feeding/Residual Contact Activity, Preventive)

24-well microtiter plate (MTP) with artificial diet was treated withtest solutions by pipetting. After drying, the MTPs were infested withL2 larvae (10-15 per well). After an incubation period of 5 days,samples were checked for larval mortality, antifeedant and growthregulation.

In this test, compounds P1, P2, P4, P5, P7, P12, P24, P29, P33, P59,P60, P61, P62, P66, P67, P68, P69, P71, P72 and P76 showed an activityof over 80% ata concentration of 400 ppm.

Example B4: Activity Against Diabrotica Balteata (Corn Root Worm)(Larvae L2 on Maize Sprouts, Feeding/Contact, Preventative)

Maize sprouts, placed on an agar layer in 24 well micro titer plateswere treated with test solutions by spraying. After drying, the MTPswere infested with L2 larvae (6-10 per well). After an incubation periodof 5 days, samples were checked for larval mortality and growthregulation.

In this test, compounds P1, P2, P5, P7, P10, P11, P15, P16, P20, P21,P22, P24, P35, P46, P48, P54, P55, P56, P59, P60, P61, P62, P63, P64,P65, P66, P67, P68, P69, P70, P71 and P76 showed an activity of over 80%at a concentration of 400 ppm.

Example B5: Activity Against Myzus persicae (Green Peach Aphid)(Feeding/Residual Contact Activity, Preventive), Mixed Population

Sunflower leaf discs were placed on agar in a 24-well microtiter plateand sprayed with test solutions. After drying, the leaf discs wereinfested with an aphid population of mixed ages. After an incubationperiod of 6 DAT, samples were checked for mortality and special effects(e.g. phytotoxicity). In this test, compounds P1, P2, P7, P8, P15, P16,P19, P20, P22, P24, P30, P33, P34, P46, P48, P53, P55, P58, P59, P60,P61, P62, P66, P68, P69 and P71 showed an activity of over 80% at aconcentration of 400 ppm.

Example B6: Activity Against Myzus persicae (Green Peach Aphid) (FeedingActivity Sachet Test), Mixed Population

Test compounds were applied by pipette into 24 well plates and mixedwith Sucrose solution. The plates were closed with a stretched Parafilm.A plastic stencil with 24 holes is placed onto the plate and infestedpea seedlings were placed directly on the Parafilm. The infested plateis closed with a gel blotting paper and another plastic stencil and thenturned upside down. 5 days after infestation the samples were checked onmortality. Application rate: 12.5 ppm.

In this test, compounds P2, P7, P15, P20, P22, P24, P30 and P33 showedan activity of at least 80% at a concentration of 12.5 ppm.

Example B7: Activity Against Myzus persicae (Green Peach Aphid)(Systemic/Feeding Activity, Curative), Mixed Population

Roots of pea seedlings, infested with an aphid population of mixed ages,were placed directly in the test solutions. 6 days after introduction,samples were checked for mortality and special effects on the plant.

In this test, compounds P2, P6, P7, P8, P14, P34, P35, P55, P58, P60,P66, P68, P69 and P71 showed an activity of at least 80% at aconcentration of 24 ppm.

Example B8: Activity Against Thrips tabaci (Onion Thrips) (MixedPopulation, Feeding/Residual Contact Activity, Preventive)

Sunflower leaf discs were placed on agar in a 24-well microtiter plateand sprayed with test solutions. After drying, the leaf discs wereinfested with a thrips population of mixed ages. After an incubationperiod of 7 days, samples were checked for mortality and special effects(e.g. phytotoxicity).

In this test, compounds P1, P2, P59, P60, P65, P67, P72 and P76 showedan activity of over 80% at a concentration of 400 ppm.

Example B9: Activity Against Bemisia tabaci (Cotton White Fly)(Adulticide Contact Activity, Preventative), Adult

Cotton leaf discs were placed on agar in a 24-well microtiter plate andsprayed with test solutions. After drying, the leaf discs were infestedwith adult white flies. After an incubation period of 7 DAT, sampleswere checked for mortality and special effects (e.g. phytotoxicity).

In this test, compounds P1, P2, P7, P8, P48, P49, P58, P59, P60, P61,P68 and P69 showed an activity of over 80% at a concentration of 400ppm.

Example B10: Activity Against Euschistus heros (Neotropical Brown StinkBug)

Soybean leaf on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10′000 ppm DMSO stock solutions.After drying the leaf were infested with N-2 nymphs. The samples wereassessed for mortality 5 days after infestation.

In this test, compounds P48, P62 and P69 showed an activity of over 80%at a concentration of 400 ppm.

Example B11: Activity Against Frankliniella occidentalis (Western FlowerThrips) (Mixed Population, Feeding/Contact, Preventative)

Sunflower leaf discs are placed on agar in a 24-well microtiter plateand sprayed with test solutions. After drying, the leaf discs areinfested with a Frankliniella population of mixed ages. After anincubation period of 7 DAT, samples are checked for mortality andspecial effects (e.g. phytotoxicity). In this test, compound P42 showedan activity of over 80% at a concentration of 400 ppm.

Example B12: Activity Against Tetranychus urticae (Two-Spotted SpiderMite)

Bean leaf discs on agar in 24-well microtiter plates were sprayed withaqueous test solutions prepared from 10′000 ppm DMSO stock solutions.After drying the leaf discs were infested with a mite population ofmixed ages. The samples were assessed for mortality on mixed population(mobile stages) 8 days after infestation.

The following compounds resulted in at least 80% mortality at anapplication rate of 400 ppm: P6, P11, P29 and P57.

Example B13: Activity Against Aedes aegypti (Yellow Fever Mosquito)

Test solutions, at an application rate of 200 ppm in ethanol, wereapplied to 12-well tissue culture plates. Once the deposits were dry,five, two to five days old adult female Aedes aegypti were added to eachwell, and sustained with a 10% sucrose solution in a cotton wool plug.Assessment of knockdown was made one hour after introduction, andmortality was assessed at 24 and 48 hours after introduction.

The following compounds gave at least 80% control of Aedes aegypti after48 hours: P60 and P62.

1. A compound of formula I,

wherein G₁ is nitrogen or CR₂; G₂ is nitrogen or CR₃; G₃ is nitrogen orCR₄; G₄ is nitrogen or CR₅; G₅ is nitrogen or CR₆, with the proviso thatnot more than 2 nitrogens as G may follow consecutively; R₂, R₃, R₄, R₅or R₆ are, independently from each other, hydrogen, halogen,C₁-C₄haloalkyl, C₁-C₄haloalkyl substituted by one or two hydroxy,C₁-C₄haloalkyl substituted by one or two methoxy, C₁-C₄haloalkylsubstituted by one or two cyano; or R₂, R₃, R₄, R₅ or R₆, independentlyfrom each other, are C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfonyl,O(C₁-C₄haloalkyl), SF₅, phenylcarbonylthio, cyano, mercapto,C₁-C₄alkoxycarbonyl, or —C(O)C₁-C₄haloalkyl; or two adjacent R_(i),wherein R_(i) is selected from R₂, R₃, R₄, R₅ and R₆, taken together mayform a fragment —OCH₂O— or —OCF₂O—; Q is a radical selected from thegroup consisting of formula Q₁ to Q₂:

wherein the arrow denotes the point of attachment to the triazole ring;and wherein X is S, SO or SO₂; each R is, independently from each other,hydrogen, halogen, C₁-C₄haloalkoxy or C₁-C₄haloalkyl; each R₁ is,independently from each other, C₁-C₄alkyl, C₁-C₄haloalkyl,C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₃-C₆halocycloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl or C₂-C₆alkynyl; and each R₇ is,independently from each other, hydrogen or halogen; and R₈ is hydrogen,C₁-C₄alkyl or C₁-C₄haloalkyl; and agrochemically acceptable salts,stereoisomers, enantiomers, tautomers and N-oxides of those compounds;with the exception of2-[5-(2,4-dichlorophenyl)-4-methyl-1,2,4-triazol-3-yl]-3-methylsulfanyl-pyridine;2-[5-(2,4-dichlorophenyl)-4-methyl-1,2,4-triazol-3-yl]-3-ethylsulfanyl-pyridine;and2-[5-(4-n-pentylphenyl)-4-methyl-1,2,4-triazol-3-yl]-3-methylsufonyl-pyridine.2. A compound of formula I according to claim 1, represented by thecompounds of formula I-1

wherein G₁, G₂, G₃, G₄, and G₅ are as defined under formula I in claim1; X₁ is S, SO or SO₂; Ra₁ is hydrogen, halogen or C₁-C₄haloalkyl; R₁₁is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl; and R₈ is asdefined under formula I in claim 1; and agrochemically acceptable salts,stereoisomers, enantiomers, tautomers and N-oxides of those compounds.3. A compound of formula I-1 according to claim 2, wherein G₁ is N, G₂is CH, G₃ is CH, G₄ is C(CF₃) and G₅ is CH.
 4. A compound of formula I-1according to claim 2, wherein G₁ is CH, G₂ is N, G₃ is CH, G₄ is C(CF₃)and G₅ is CH.
 5. A compound of formula I according to claim 1represented by the compounds of formula I-2

wherein G₁, G₂, G₃, G₄, and G₅ are as defined under formula I in claim1; X₂ is S, SO or SO₂; Ra₂ is hydrogen, halogen or C₁-C₄haloalkyl; R₁₂is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl; R₈ is asdefined under formula I in claim 1; and agrochemically acceptable salts,stereoisomers, enantiomers, tautomers and N-oxides of those compounds.6. A compound of formula I-2 according to claim 5, wherein G₁ is N, G₂is CH, G₃ is CH, G₄ is C(CF₃) and G₅ is CH.
 7. A compound of formula I-2according to claim 5, wherein G₁ is CH, G₂ is N, G₃ is CH, G₄ is C(CF₃)and G₅ is CH.
 8. A compound of formula I according to claim 1,represented by the compounds of formula I-3

wherein A is N or CH; R₁₀ is phenyl mono- or polysubstituted bysubstituents independently selected from the group consisting ofhalogen, cyano, C₁-C₄haloalkoxy, C₁-C₄alkoxycarbonyl or C₁-C₄haloalkyl;or R₁₀ is phenyl substituted by a fragment —OCF₂O— on two adjacentpositions; or R₁₀ is pyridyl mono- or polysubstituted by substituentsindependently selected from the group consisting of halogen, cyano,C₁-C₄haloalkoxy or C₁-C₄haloalkyl; or R₁₀ is pyridyl substituted by afragment —OCF₂O— on two adjacent positions; X₃ is S, SO or SO₂; Ra₃ ishydrogen, C₁-C₄haloalkoxy or C₁-C₄haloalkyl; R₁₃ is C₁-C₄alkyl orC₃-C₆cycloalkyl-C₁-C₄alkyl; and R₈ is hydrogen or C₁-C₄alkyl.
 9. Acompound of formula I according to claim 1, represented by the compoundsof formula I-4

wherein A is N or CH; R₁₀′ is a diazine radical selected from the groupconsisting of formula DA1 to DA5,

wherein the arrow denotes the point of attachment to the triazole ring,and said group R₁₀′ may be mono- or polysubstituted by substituentsindependently selected from the group consisting of halogen, cyano,C₁-C₄haloalkoxy or C₁-C₄haloalkyl; X₄ is S, SO or SO₂; Ra₄ is hydrogen,C₁-C₄haloalkoxy or C₁-C₄haloalkyl; R₁₄ is C₁-C₄alkyl orC₃-C₆cycloalkyl-C₁-C₄alkyl; and R₈ is hydrogen or C₁-C₄alkyl.
 10. Apesticidal composition, which comprises at least one compound of formulaI according to claim 1 or, where appropriate, a tautomer thereof, ineach case in free form or in agrochemically utilizable salt form, asactive ingredient and at least one auxiliary.
 11. A method forcontrolling pests, which comprises applying a composition according toclaim 10 to the pests or their environment with the exception of amethod for treatment of the human or animal body by surgery or therapyand diagnostic methods practised on the human or animal body.
 12. Amethod for the protection of plant propagation material from the attackby pests, which comprises treating the propagation material or the site,where the propagation material is planted, with a composition accordingto claim
 10. 13. Plant propagation material treated in accordance withthe method described in claim
 12. 14. A compound of formula (X)

wherein Q and R₈ are as defined under formula I in claim 1; and L_(G) isiodine or bromine.
 15. A compound of formula (XII)

wherein Q and R₈ are as defined under formula I in claim 1.